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FEATURE F E ARTICLE

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s supram molecula ar syste ems upo on exog genous s stimulli Cheng g-Peng Li,a Jing Ch en,a Chun n-Sen Liub and Miaao Du*,a a

College off Chemistry, Tianjin Key y Laboratory ry of Structu ure and Perfformance foor Functiona al Moleculess,

MO OE Key Lab boratory of Inorganic-O I Organic Hyb brid Function nal Materiall Chemistry,, Tianjin No ormal Univerrsity, Tianjin T 3003 387, P. R. C China. E-ma ail: dumiao@ @public.tpt.ttj.cn. b

Henan Provvincial Key Laboratory of Surface & Interface Science, Zhengzhou Z U University of o Light Indu ushou 450002 2, P. R. Chin na trry, Zhengzh

Table o of Contentts Entry

Th his feature arrticle comme ents on the dynamic strructural trans sformations of coordinaation supram molecular sysstem ms in the asspects of me etal node, organic linker,, porosity, and framework, which caan be triggerred by various exogenous stimuli, such as a concentra ation, tempe erature, light, mechanica al force, andd their synerg gistic effect.

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Dynamic c structural tra ansform mations of coorrdinatio on

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FEATURE ARTICLE

Cite this: DOI: 10.1039/x0xx00000x

Dynamic structural transformations of coordination supramolecular systems upon exogenous stimuli

Received 00th xxxx xxxx, Accepted 00th xxxx xxxx DOI: 10.1039/x0xx00000x www.rsc.org/

Reaction in the solid state, especially single-crystal-to-single-crystal (SC-SC) transformation, provides an appealing routeway to obtain the target crystalline materials with modified properties via a non-solvent green chemistry approach. This feature article focuses on the up-to-date progress in the context of coordination supramolecular systems (CSSs), especially coordination polymers (CPs) or metal-organic frameworks (MOFs), which show interesting dynamic nature upon various exogenous stimuli, including concentration, temperature, light, mechanical force, as well as their synergic effect. In essence, dynamic CSSs normally possess crucial crystallinereactive characteristics: i) metal ions or clusters with unstable or metastable electronic configurations and coordination geometries; ii) organic ligands bearing physicochemically active functional groups for post-reactions; iii) polymeric networks of high flexibility for structural bending, rotation, swelling, or shrinking; iv) guest moieties to be freely exchanged or eliminated by varying the environmental conditions. The significant changes in catalytic, sorption, magnetic, or luminescent properties accompanied by the structural transformations will also be discussed, which reveal the proof-of-concept thereof in designing new functional crystalline materials.

Introduction

have extensively taken advantage of the solid phase reactions to produce the targeted compounds, and obtained a deeper underReaction, in three states of matter, is the fundamental theme to standing on the nature of such reactions. These excellent breakchemistry and life course.1 These dynamic processes generally throughs have not only made a promise to get the materials that involve the formation and breakage of covalent or noncovalent may be impossible to obtain via the reactions in solvent media, interactions, by regulating the local binding features of individ- but also provided an opportunity to modify their bulk physicoual ingredients and the overall structural extension/stacking in chemical properties through the solid-state reactions. Of significant necessity, it should make no confusion on the crystalline state.2 In the state of solution or gas, molecules are endowed with large freedom to disperse and move, which facil- definition of the topotactic reaction and single-crystal-to-singleitates the homogenous reactions between the functional groups crystal (SC-SC) transformation here. The term of topochemical of reactants. However, reactants in solid phase have more con- principle was firstly proposed by Kohlschüetter to describe the finement of arrangement and less freedom of movement, owing inorganic crystal transformation,6 that is, a reaction in inorganic to the frustrating effect of molecular closing packing. It is felic- crystal can occur wherein the crystal lattice of starting reactant itously and vividly remarked by Leopold Ruzicka ― a crystal is (mother crystal) determines the orientation of at least one crysa chemical cemetery. That is, in contrast to liquid and gas states, tallographic axis of the product crystal (daughter crystal). This molecules in the solid state, especially crystalline state, are rig- phenomenon in inorganic system is described by topotaxy, and idly and steadily fixed within the lattices to show a nearly life- such a reaction is a topotactic reaction. With regard to an SC-SC less nature.3 Thus, the reacting functional groups in solid phase reaction, it is unnecessary to require a perfect lattice consistengenerally behave the inert features due to their restricted migra- cy on at least one crystallographic axis between the mother and tion and non-aligning orientation. Nevertheless, chemical reac- daughter crystals, which however will make an emphasis on the tions in the solid state are not unachievable and a large number unanimous single-crystallinity with no disintegration.7 In pracof inorganic and organic compounds can feature regioselective- tice, this term is preferred to be applied in organic or inorganicly and stereospecifically structural transformations upon exoge- organic hybrid systems. At this stage, coordination supramolecular systems (CSSs), nous stimuli in the solid state.4 Early in the 1960s, Schmidt has presented the concept of crystal engineering in domain of solid- especially coordination polymers (CPs) or metal-organic framestate organic photochemistry, in order to erect a bridge between works (MOFs),8 are quite appealing, because of their structural the structure and reactivity of molecules.5 Since then, chemists aesthetics9 and remarkable properties for potential applications

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Cheng-Peng Li, Jing Chen, Chun-Sen Liu and Miao Du*

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Fig.. 1 Schematic diagram for dynamic structural transformations of coordination n networks trigg gered by differennt exogenous sttimuli.

in adsorption, a co onductivity, ch hirality, magneetism, catalysi s, and opttics etc.10–13 In n fact, one of th he most interesting characterristics for CSSs is their flexible and dynamic d naturee, which is prooperly a reesult of the sy ynergistic effect of multifun nctional organiic tecton ns and predefin ned metal moieties, normally as the secoondary buiilding units (S SBUs). Thus, dynamic d structtural transform mation in the t solid state,, especially SC C-SC transform mation upon eexogenou us stimuli, hass been well ex xploited to enh hance their divversity and d functionality y (Fig. 1). Sin ngle-crystal X--ray crystalloggraphy is the t principal m method for uneequivocally determining the structurees before and after the structural transform mation. Advannces in thee instrument caapabilities faciilitate the rapid d collection off data, pow werful data pro ocessing, accu urate structurall determinationn, and con ntrollable testing environment (temperaturre and pressuree etc.), plaacing a much h higher level off proof on thee dynamic struuctural tran nsformations. Although preservation of th he single crysttalline natture is the prerrequisite here,, such modern n instruments eensure thaat the size or q quality of a sin ngle crystal suiitable for X-raay diffracction analysis will be of mu uch less strict restriction thaan beforre.14 On the oth her hand, the results r of singlle crystal diffraaction aree time/space-av veraged and origin/end-emp o phasized, whiile the pro ocesses of dynamic transform mations may considerably c ddeviate from the averagee and unexpecttedly suffer the mutation. Tooward thiss circumstancee, in situ X-raay diffraction is to be utilizeed, so thaat the trace of molecular mo otions can be directly and ppersisten ntly observed to reveal the reeaction mechan nism on the baasis of stru uctural inform mation.15 Recen ntly, Kawano et al have succcessfullly utilized the ab initio pow wder X-ray difffraction (PXRD D) for stru uctural charactterization of th he kinetic miccrocrystals.16 K Kaupp et al a have used aatomic force microscopy m (A AFM), grazingg inci-

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dencee X-ray diffra action (GID), aand scanning near field opttical 17 micro oscopy (SNOM M) to study thhe solid-state reactions. r Additionaally, some othe er techniques ssuch as thermo ogravimetry (T TG), differrential thermal analysis (DT TA), differentiial scanning calorimettry (DSC), nuc clear magneticc resonance (N NMR), X-ray phop toelectron spectrosscopy (XPS), and scanning electron microscopy (SEM) with energy e disperssive X-ray speectroscopy (ED DX) have also been app plied as the hellpful tools to monitor m the so olidstate structural tran nsformations. In n the past few decades, seveeral excellent reviews r have been b publiished, covering g the vast areaa of dynamic behaviors b of CSSs. C Particcularly, two re eviews by Vitt ttal in 2007 an nd 2013 presen nted the comprehensive accounts on ssupramoleculaar structural traansformations involvin ng CPs in the solid state.18 MacGillivray M e al et descrribed how to achieve a the suppramolecular control c of reacctivity in n the solid statte using moleccules and self--assembled MO OFs as tem mplates.19 Rec cent advances on the reactio ons of single crystals for f inorganic and a organomeetallic compou unds and their implications for catallysis were reviiewed by Frecch20a and Kaw wano 15 and Fujita. F Nassimbeni et al20bb focused on gu uest exchangees in crystalline-state CS SSs, and Zhanng et al21 prov vided an overv view on so olvent-induced d magnetic chaanges in SC-SC C transformatiions. Lauh her et al22a and d Garcia-Garibbay22b emphasized the desig gned strateegy on SC-SC C topochemical al polymerizatiion. Bharadwaaj et al preesented an acc count on the suubstitution at metal m ions of CPs in SC C-SC transform mations.23 Ferrraro et al summ marized the so olidstate pressure effec ct on stereochhemically nonrrigid structures.24a Braga et al reviewe ed the mechannical forces ind duced reaction ns in molecular crystals..24b Kawano eet al outlined the t advancemeents of ab b initio PXRD structural deteermination on kinetic coord dina-

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tion n networks.16 Notably, the special s issue of o “single crysstal to single crystal traansformations”” with some informative i reeviews in Australian A Jou urnal of Chem mistry makes an a outstandingg contrib bution on this topic.7,25,26 However, most of the review ws and exaamples availab ble in the literratures are limited to focus oon the finaal outcomes of structural traansformations, that is, the chhanges of crystal c structu ures and properrties (i.e. color, magnetism, luminesscence, chiraliity, or porosity y). In fact, the dynamic behaaviors of CSSs invariab bly originate from f differentt exogenous sttimuli and d such solid-sttate reactions can c also be considered as stiimuliresponsive propeerties of such crystalline c matterials.18b Cleaarly, it is of o great essencce to summarizze and classify y the various oorigins of solid-state reaactions, and to elucidate the discipline of rresultantt dynamic stru uctural transforrmations. Thus, in this articlle, we willl categorize th he dynamic sttructural transfformations off CSSs by exogenous stiimuli, and prim marily discusss the changes oon the buiilding units (m metal node and d ligand linker)) as well as poorosity fun nction and fram mework twistin ng in this courrse. Some structu ural characterisstics can be fou und for CSSs w which posssess the poten ntial capability y of crystallinee reactivity: i) metal ion ns or clusters w with unstable or metastable electronic connfiguratiions and coord dination geom metries; ii) orgaanic ligands beearing phy ysicochemicallly active group ps for post-reaactions; iii) poly lymeric networks n of hig gh flexible natu ure for structurral bending, rootation, sweelling, or shrin nking; iv) lattiice guests to be freely removved or excchanged. In th his context, thee delicate selection of stimuulation willl play a critical role to effecctively inducee the dynamic structuraal transformattions for speciific coordinatio on systems. H Herein, we will commentt on dynamic structural s transsformations off CSSs upo on diverse exo ogenous stimu uli, including concentrationn, heat (tem mperature), lig ght, mechanical force, as weell as their synnergic infl fluence. Notably, most of thee examples preesented in thiss work willl be subject to o drastic strucctural changes, normally wiith the forrmation and brreakage of cov valent or nonco ovalent interacctions.

Dy ynamic stru uctural tran nsformations induced d by Co oncentratio on Sollid-state structtural transform mation can be induced i by thee concen ntration enviro onment of a ceertain componeent inside or ouutside thee material, maiinly involving guest (solventt, gas, anion, oor free mo olecule) sorptio on or exchange, post-synthetic exchange ((PSE), and d post-synthettic modificatio on (PSM). Off great significcance, succh dynamic pro ocesses are ussually accompaanied by channges in botth crystal strucctures and prop perties. Gu uest adsorptio on or exchang ge. Molecular cages can seleectively capture c guestss in solution viia specific hosst-guest interaactions and d molecular reecognitions.2a,227 While in the solid state, paarticularlly in the crystaalline state, thiis is often invaalid due to thee close paccking nature of crystal. Fujitta et al successsfully combineed the mo olecular cages into crystallin ne CPs to tran nsfer the richnness of solution-state ho ost-guest chem mistry into soliid state.28 An interestiing example w was illustrated d in [Co3(SCN N)6(tpt)4]n coorrdination n network (1),, where tpt = 2,4,6-tris(4-py 2 ridyl)-1,3,5-trriazine, wh hich behaves aas a crystallinee molecular sponge engineerred on thee molecular lev vel for guest recognition r sim milar to those found

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ChemCom mm in solution. This ne etwork is consstructed from the infinite arrrays of occtahedral Co6(ttpt)4 cages arraanged in a meetal vertex-sharring View Article Online fashion, defining th he void spacess with alternat ing cuboctahedral DOI: 10.1039/C4CC06263A Co12(tpt) ( 8 and Co122(tpt)24 cages ((Fig. 2). When n soaked in a saturated d toluene solutiion of tetrathiaafulvalene (ttff), the cages co ould be acctivated to adsorb four ttf moolecules, and the t crystal sysstem flexib bly changes frrom cubic to teetragonal. How wever, the enccapsulatiion of Ph2NH into the crystaalline cages will w not changee the cubicc framework. Moreover, M thee nanoscale voids can adsorb b up to an n impressive 35 5 wt% of C60 oor C70 by soak king the crystalls in a tolu uene solution of fullerene. Remarkably, a preferential adsorpttion of C70 ove er C60 is also observed wheen the crystals are immeersed in a mixed solution off C60/C70 fullerrenes.

Fig. 2 Structural tran nsformations off 1 upon the incclusion of tetratthia28 8 fulvalene or Ph2NH.

As A one of the most m interestinng characters of o CPs, the breathing phenomenon p iss often observeed, when a fraamework preseents multiiple stable stattes to fabricatee the flexible pores p with diverse shapees and sizes fo or guest sorptiion.29 Upon in nclusion of diffferent guests, g such crrystalline mateerials can show w specific fraamework k flexibility in the solid statee. Zhang et al studied the fllexibility y of a series off isoreticular [M M3(μ3-OH)(L))3]n framework ks30a 31 with the (3,9)-conn nected xmz toopological netw work, which h are consttructed by 3-c connected, trippodal pyridyl-d dicarboxylate ligands and 9-connected, tricappedd trigonal-prism matic M3(μ3-O OH)C 6(py)3 clustters (Fig. 3). P Powder and sin ngle-crystal X-ray (O2CR) diffraaction analyses indicate thatt [Ni3(μ3-OH)((cpby)3]n (2, cpby c = 2,6 6-di-p-carboxy yphenyl-4,4’-bbipyridine) can n drastically sw well 70–105% in volum me and 75–1211% in length upon u accommo odation of o different solvents, includiing pyridine, 1,4-dioxane, 1 D DMF, DMA A, EtOH, MeO OH, and water.. The thermal expansion coeefficient of 2∙DMF is extremely larrge up to 437 7 × 10–6 K–1 upon u inclu usion of DMF at a 295 K. The distinct breath hing effects off the

Fig. 3 Perspective view of the (3,9)-cconnected xmz framework. f

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fram meworks are m mainly due to the organic lig gand of cpby w with a suitable backbon ne. Lee, Lah, and a Vittal et all reported a sooft CP, {[Z Zn(pnmi)](solv vent)}n (3, pnm mi = N-(4-pyrridyl)-1,4,5,8-nnapha thaalenetetracarbo oxymonoimidee) with the rtll topology bassed on pad ddle-wheel Zn n(O2CR)4(py)2 SBUs.30b Thee 1D rhombic channells can show th he flexible breaathing effect to t exchange thhe solven nts in SC-SC ffashion, with the t SBUs rem maining intact. Upon excchange with D DMF, EtOH, etthylene glycoll, triethylene gglycol, or allyl alcohol, the reduction in unit cell volume and thee void vollume will be u up to 16% and 33.1%, respecctively. To serve as th he outstanding g chemosensorrs, CSSs can eexhibit gueest-responsivee structural traansformations (even in tracee concen ntration) and tthe changes off physical prop perties (color, magnettism, and electtric resistance)) facilitate the sensitive and selectivee detection of gas- or vaporr-phase analytees for applicattion in cheemical threat aalert, medical diagnostics, thermal batteryy, and env vironmental m monitoring.32 Yaghi Y et al pro oposed three crriteria forr high perform ming porous materials in watter sorption, inncluding g condensation n pressure of water w in the po ores, the uptakke capaccity, and recycclability and water w stability of o the materialls.33 A com mparison of w water sorption properties of 23 2 porous matterials rev veals that theirr performancess can be well-d defined by inttermolecular interactio ons between th he adsorbed waater moleculess. Blue block ccrystals of {[C Co1.5(tipb)(SO4)(tp)0.5](DMF F)1.75}n (4∙D DMF, tipb = 1,3,5-tris(p-im midazolphenyll)benzene, tp = tereph hthalate), synth hesized by Bu u et al, exhibit the self-penettrating nettwork with 1D D ultramicropores for the inclusion of DMF F (Fig. 3 4).34 When thesee crystals are exposed e to air, they gradually ly turn to red r in the SC-SC transformaation, affordin ng a 2-fold inteerpenetraating network of {[Co1.5(tip pb)(SO4)(H2O))3.6](tp)0.5(solvvent)}n (4∙H H2O). During this transform mation, water ligands l displacce tp2– ligaands and the ccoordination geometries g of Co(II) changee from tetrrahedral to octtahedral, which h induce an ob bvious color chhange from blue to red.. Notably, the framework ch hanges from nneutral to cationic, and tthe tp2– anion ns are randomlly distributed in the chaannels to main ntain a charge balance. Simiilar structural transforrmation can alsso be stimulated by NH3. Of great significcance, 4∙D DMF can effecctively encapsulate DMF mo olecules and reelease theem in the preseence of water vapor v (in humidistat) or watter (by imm mersion) in SC C-SC transforrmation, reveaaling the gate effect forr controllable g guest trapping g and release. Such S gate effeect for seleective adsorpttion of solvents is usually fou und in the dynnamic

CPs with w hemiopen n channels.35 Z Zeng and Kurm moo et al reported a 4-ffold interpenettrating pseudoodiamond coorrdination netw work View Article Online {[Co(pybz)2](DMF F)2}n (5∙DMF,, pybz = DOI: 4-(4-10.1039/C4CC06263A pyridyl)benzo oate), which h can be transsformed upon exchanges wiith MeOH, EtO OH, benzeene, or cycloh hexane in diffeerent concentrrations, showin ng a vapochromism SC-SC process.366 The vapochrromism phenomenon can c be ascribed to the modiffication of coo ordination geometry, from f a very strrained octaheddron with two chelating carb boxylate groups to a more m relaxed ooctahedron with unidentate carboxy ylate and waterr ligands, whicch results in a change in ligaandfield energies of the d orbital of C Co(II) ion. No otably, besidess the chem mical sensors of o CSSs to hum midity,37 some excellent prototypess for such CSS Ss sensors to aalcohols,38a,38bb formaldehydee,38c nitroaaromatic comp pounds,38d oxyygen,38e chrom mophores38f and d so on, were w also documented.

Fig.. 4 Reversible SSC-SC transform mations between n the self-penettrating

Fig. 5 A cationic poro ous CP with the exclusive anion n-exchange for OAc O – – – 40c over Cl C , BF4 , and NO O3 anions.

and d 2-fold interpen netrating frameworks.

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Anio on exchange. When W neutral organic ligand ds are used forr the assem mblies of CSSs, the cationic host framewo orks will norm mally be fo ormed and corrrespondingly, the anions mu ust be involved to balan nce the charge e.39 The interac actions betweeen the host fraamework ks and anions, such as coorddinative bond, H-bonding in nteraction n, and electrostatic force, m may provide good opportuniities for an nion chemosensors based onn anion-exchaanged approaches. Bu et al reported a 4-fold interppenetrating coordination fraamework k {[Cu(pytpy)]](NO3)(CH3OH H)}n (6∙NO3, pytpy = 2,4,6-tris (4-py yridyl)pyridine e), which can sserve as a nak ked-eye colorim metric seensor for differrent anions succh as F–, Cl–, Br B –, I–, N3–, SC CN–, 2– 40a and CO C 3 . Ghossh et al preparred a dynamic luminescent catic onic porous framew work, which hhas the order of o affinity to gu uest anion ns (SCN– > N3– > N(CN)2– > ClO4–) owin ng to their variious sizes, shapes, geom metries, coordiination tenden ncies to metal ions, i as weell as the distinct π∙∙∙π interaactions and H-bonding H abiliities with the host netw work.40b We syynthesized two o isostructural 3D 242 CPs {[M(L )2](ClO4)2}n (7∙ClO O4, MII = CdII or ZnII, L242 = 4(4-py yridyl)-3,5-bis(2-pyridyl)-1,22,4-triazole), which w have 2-fold interp penetrating lvtt networks andd exhibit the exclusive e and irrei versib ble anion-exch hange behavioor toward acetaate (Fig. 5) wiith a structural change.40c Also, other anion chemossensors and seelec40d-40h h tive anion-exchang a ged materials oof CSSs were reported. r



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The hazard-fr free treatment on waste wateer with metal ppollutan nts, normally in n their oxo-/h hydroxo- anion nic forms, inclluding AsO O43–, TcO4–, S SeO32–, CrO42–, Cr2O72–, ReO O4–, and MnO4 –, is a wo orldwide problem that is listted as prioritiees by the U.S. Envi4 ron nmental Protecction Agency.41 Many effortts have been ddevoted in designing m materials with good selectiviity and efficienncy to thiss end. In this point, organicc polymer-baseed bifunctionaal anion--exchange resiins show limitted application ns due to theirr poor theermal and chem mical stability y.42 Recently, a series of inorrganic DHs), aniion-exchanged d materials, lay yered double hydroxides h (LD were prepared by y Albrecht-Sch hmitt and Oliv ver et al, whicch can rap pidly capture th he target oxoaanions with hig gh exchange caapaci4 ty.43 Cheng44a an nd Wang44b et al prepared tw wo 3D porouss cationiic MOFs, with h fast exchang ge, high capaciity, and good selectiviity for the cap pture and separration of CrO42– and Cr2O72–, even in SC-SC S transfo ormations, whiich can be asccribed to the sttronger interactions i beetween the oxo oanions and caationic framew works. Reccently, we obttained a 3D caationic framew work with 1D pporous chaannels, i.e. {[A Ag(L243)](CHC Cl3)(ClO4)}n (8 8∙ClO4, L243 = 3-(2pyrridyl)-4-(4-pyrridyl)-5-(3-pyrridyl)-1,2,4-triiazole), showinng the

ChemCom mm eatures in SC- SC transformaations induced d by remaarkable dual fe exchaanging the inc cluded ClO4– aanions with different toxic oxoo View Article Online metal anions (Fig. 6).45 On the oone hand,DOI: 8∙C10.1039/C4CC06263A lO4 possesses the rigid nature to be partially p exchaanged with MnO M 4– in waterr so243 lution n, affording a new product {[Ag(L )](C ClO4)x(MnO4)1–x}n (8∙CllO4∙MnO4), allong with a cleear color chan nge from colorrless to pu urple. On the other o hand, 8∙C ClO4 shows th he flexible naature to cap pture CrO42– anions, in whicch the CrO42– anions a are dyn namically y transformed into Cr2O72– an anions. Also, th he pores shrin nk in the c axis to facilita ate the formati tion of coordin nation interactiions between Ag(I) cen nters and Cr2O 72– anions, resulting in a squ uare pyram mid coordinatiion geometry oof Ag(I) ion in n the yellow crystal off {[Ag(L243)](C Cr2O7)1/2}n (8∙C Cr2O7). In watter solution, fo orms of Crr(VI) existence e can be well rregulated by pH p condition, that is, CrrO42– and Cr2O72– are predoominant in a basic b environm ment and in i pH 2–6, resp pectively.46 Thhis is the first example of MOF M molecular flask forr catalyzing suuch an inorgan nic reaction. So ome crystalline materials reported byy Hou,47a Zeng g,47b and Pan and Su47cc et al can act as the hosts ffor trapping vaarious iodine spes cies, which is also a prominent pproblem in watter pollution.

Fig. 6 A 3D cationic fframework showing the dual beha aviors in SC-SC traansformations induced by anion-e exchange. 424 A 3D MOF {{[Ag(L424)(H2O)](NO O = 33,5-bis 3)}n (9∙∙NO3, L (4-pyridyl)-4-(2-pyridyl)-1,2,4 4-triazole) with h 1D channels along thee c axis for the inclusion of NO N 3– also show ws the dual dynnamic SC C-SC transform mations induceed by anion-exchange stimulli.48 In thiss structure, thee tetrahedral Ag(I) A ion is surrrounded by thhree N ato oms and one w water ligand, an nd the overall network show ws a 3fold d interpenetraating lvt patterrn. When exch hanged by NO O2–, the pro oduct {[Ag(L4224)(NO2)](H2O) O 1.5}n (9∙NO2) also takes a 33-fold inteerpenetrating fframework, bu ut with the breeakage of Ag– Owater bon nds and the forrmation of Ag g–Onitrite interacctions. Howevver, by imm mersing in CF F3COO– solutio on, the coordiination environnment of Ag(I) A in 9∙NO O3 is completed d by CF3COO– instead of waater to affo ford 9∙CF3COO, accompaniied by a chang ge of the interrpenetratting pattern frrom 3-fold to 2-fold 2 during this SC-SC prrocess (Fig. 7). Zhang eet al reported a series of naanoporous netw works con nstructed by a polycatenated d isoreticular 1D ribbon of rings, and d their pore sizzes or shapes can c be system matically adjustted by

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a e processes, w which allow the dynamic trrans the anion-exchang formations between n the interpene netrating net structures in difffer49 ent dimensions. d These T materialls can also be post-syntheticcally modiified by SC-SC C [2+2] photoopolymerizatio on, to reinforcee the porou us frameworkss through the ccovalent locking effect and also, a affect their adsorpttion propertiess.

Fig. 7 A 3D cationic framework show wing the dual dy ynamic behaviors of SC-SC C transformation ns upon differennt anion-exchange processes.

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Post-synthetic eexchange (PSE E). CSSs are normally n assem mbled in one-pot o solvotthermal syntheesis, where stru uctural regulattion is reaalized by the d delicate choice of metal ions, organic linkeers, or syn nthetic routes. Recently, the sophisticated synthetic straategies were developed tto achieve mu ultifunctional hybrid h materiaals via step pwise reaction ns of CSSs.50 These PSE strrategies involvve the meetathesis of org ganic linkers as a well as metal ions in the SBUs (Fig. 8), which aare normally observed o in so olvent-mediateed solid-solid reactionss and solid-liqu uid conditionss. As for metath hesis of organ nic linkers, sollvent-assisted linker excchange (SALE E) provides a promising p app proach that invvolves exp posing parent crystalline maaterials to a co oncentrated soolution

Feature ARTIICLE of acccessional orga anic linkers inn a specific sollvent. As a ressult, the daughter d materrials possess thhe same frameeworks as the parp View Article Online ent ones but with distinct d organicc linkersDOI: comi ing from the so olu10.1039/C4CC06263A tion. In the early 1990s, Robsonn et al proposeed the SALE conc 5 cept,51a and Kitagawa51b and Cheen51c et al succcessfully obtaiined the 3D targeted nettworks by linkking the 2D paaddle-wheel lay yers by biipyridyl pillarss. Then, Zhou et al extended d this strategy into molecular metal-orrganic polyheddra (MMOP).51d Also, Choee,51e Coheen,51f and Hupp51g et al impllemented SAL LE for chemiccally inert MOFs, which h currently arisses an intense interest in exp ploitation n of PSE.

Fig. 8 Schematic view w of the PSE strattegy.

In 2012, Hup pp et al reporteed the first ex xample of SAL LE for zeo olitic imidazollate framework ks (ZIFs).51g Immersing I thee crystal sample of [Cd d(eim)]n (10∙C CdIF-4, eim = 2-ethylimidazzolate) into o solutions containing the excess e 2-nitroim midazole (nim m) and 2-m methylimidazo ole (mim), resp pectively, will give two daugghters ZIF Fs, [Cd(nim)]n (10∙CdIF-9) and [Cd(mim m)]n (10∙SALE EM-1) of RHO R zeolitic ttopology in an n SC-SC SALE E process. It iss notewo orthy that 10∙S SALEM-1 can nnot be directly y prepared froom the org ganic ligands aand metal ionss. Further, the dpea linker (ddpea = meso-1,2-di(4-py yridyl)-1,2-eth hanediol) with a length of caa. 9 Å in SALEM-5 S can n be readily reeplaced by the 11-Å pillar off 4,4’(2,3 3,5,6-tetrametthyl-1,4-pheny ylene)dipyridin ne, 14-Å pillarr of 2, 6-d di(pyridin-4-yll)naphthalene, and 17-Å pilllar of 4,4’-((2,,3,5,6tetrramethyl-1,4-p phenylene)bis((ethyne-2,1-diyl))dipyridinee at the reaasonable rates to form SALE EM-6, SALEM M-7, and SAL LEM8, respectively r (F Fig. 9).52a Of further f significcance, such a sstrategy can also be feeasible in conttrolling over th he net catenattion in pilllared paddle-w wheel MOFs. That is, SAL LE-generated M MOFs sho ow the noncateenated structurre, while the de d novo syntheesized 52b anaalogues have tthe 2-fold interpenetrating patterns. p Lahh et al rep ported the SAL LE reactions of o [Ni(Hbtc)(b bpy)]n (11a, H3 btc = 1,3,5-benzenetriccarboxylic acid, bpy = 4,4’--bipyridine) byy 1,4diaazabicyclo[2.2.2]octane linkeer (dabco) to afford a two dauughter maaterials with th he formulae [N Ni(Hbtc)(dabco o)]n (11b) andd [Ni2(Hb btc)2(bpy)0.6(d dabco)1.4]n (11cc).53 In these transformation t ns, the enttropically favo orable productt 11b with com mpletely exchhanged

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o and the enth halpically favoorable species 11c with partiially dabco exchaanged bpy/dab bco in the alteernating layerss, can be obtaiined by co ontrolling the concentration c of dabco. Rossi et al utilized d the SALE E strategy to prepare p a seriees of isoreticullar bio-MOF--100 crystals with progrressively longeer dicarboxylaate linkers.54 CorC respo ondingly, the products p show w the progressiively larger meesoporou us cavities, wiith pore sizes rranging from 2.1 to 2.9 nm and surfaace areas rangin ng from 2704 to 4410 m2/g.

Fig. 9 Insertions of progressively p lonnger ligand pilla ars into the pilla ared paddle-wheel structu ures of MOFs thrrough SALE stra ategy.

52a

Metathesis M of metal m centers in CSSs was in nitially investigated by y Long, Hou, and a Zaworotkko et al, revealling the feasibiility of paartial metal exc change throughh SC-SC transsformation.55 Kim K et al reported the fiirst example S SC-SC transforrmation involv ving

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com mplete and rev versible exchan nge of metal ions (Cd2+ andd Pb2+) 56 in MOFs. M Some excellent wo ork on this sco ope of researcch was rev viewed by Hup pp and Farha in i 2013.57 Nottably, Zaworootko et al synthesized s a unique porphy yrin-encapsulaating MOF maaterial {[C Cd4(bpt)4[Cd(p porph)(solventt)](solvent)}n (12∙Cd∙Cd-p porph, bptt = biphenyl-3 3,4’,5-tricarbox xylate), which h can be stepw wisely tran nsformed into o 12∙Cu∙Cd-po orph and 12∙C Cu∙Cu-porph h upon tran nsmetalation rreaction in the SC-SC modee (Fig. 10).58 D During thiss transformatio on, the binucleear [Cd2(COO O)6]2– unit will suffer a trransformation into the tetran nuclear [Cu4X2(COO)6(solvvent)2] (X = anion) unit,, resulting in a 20% unit celll expansion, hhigher surrface area, and d larger pore siize in the 12∙C Cu∙Cu-porph materiall. Moreover, C Cohen et al dev veloped the geeneral tandem m strategy y for exchangee of metal ionss and organic linkers l conseccutively in i MOFs, whiich will also be helpful to th he research on prob58 ing g the chemical dynamics of MOFs. M

ChemCom mm Hupp H et al repo orted an noninnterpenetrating g MOF, with 4,4’4 (2,5-d divinyl-1,4-ph henylene)bis(33-vinylpyridinee) as organic strut, s View Article Online to wh hich the Ru-ba ased olefin meetathesis cataly yst can function to DOI: 10.1039/C4CC06263A produ uce a PSM-tra ansformed MO OF with the po olycyclic arom matic hydro ocarbon pillarss (Fig. 12).60a Such a PSM reaction r can occcur in thee solid state and a the final pproduct cannott be isolated from fr the so olution reactio on. Rosi et al ssuccessfully in ntroduced variious active groups into the pore wallss of azide-functionalized MOF, M to promote the stra aightforward ccoupling of bio omolecules to the pore walls.60b Cui et e al utilized th the PSM strateegy, replacing one proto on of the dihydroxyl group in enantiopure 2,2’-dihydro oxy1,1’-b biphenyl pillarrs by Li+ ions,, to synthesizee a highly efficcient and recyclable r hete erogeneous cattalyst for asym mmetric cyanaation of ald dehydes with up u to >99% eee.60c

Fig. 12 2 PSM reaction ca atalyzed by Ru-baased olefin metatthesis catalyst.

Fig. 10 The stepwisee transformation of porphyrin-enccapsulating MOF upon 58 nsmetalation reacction as well as th he structural changes of SBUs. tran

Post-synthetic m modification (PSM). ( PSM refers r to the cchemical modification of organic lin nker or metal node n in coordinnation nettwork, which ccan be consideered as a facilee approach to oobtain mu uch sought-afteer extended fraameworks (Fig g. 11). Modificcation on organic struts is to recover the t internal reaactive functionnality, intrroduce externaal functional groups, g or captture additional al metal ions i with unreeacted group, which w usually cannot be achhieved in de d novo MOF synthesis. It should s be noteed that the exccellent wo ork on PSM tilll 2012 has beeen reviewed by y Cohen,59 andd thus herrein we only co oncern some uncovered u examples.

60aa

Dalgarno D and Thallapally T ett al reported an a anionic fraamework k {[Mn3(tcom)2]∙[NH2(CH3)22]2∙(solvent)}n (13∙Mn, H4tccom = tetrrakis[4-(carboxyphenyl)oxam methyl]methane acid), whicch is transformed into a neutral heteroobimetallic coo ordination sysstem {[Mn nCo3(tcom)2(H H2O)2](solvent) t)}n (13∙Mn∙Co).61a In this SCSC trransformation, one terminall octahedral Mn M 2+ ion becom mes tetrah hedral geometrry and then is replaced with h the inserted Co C 2+ ion with w octahedra al sphere, whicch is accompaanied by cooperative bond b breakage e and formationn. Of further interest i is that this materrial has highly y selective cappture of divaleent transition metm als (C Co2+ and Ni2+) over alkali m metals (Li+ and Na+). A sim milar SC-S SC transformattion of PSM w was also demon nstrated by Taao et al, where w a post-sy ynthetic uptakee of free {Co3O} metal clussters with Co3O(CO2)6 SBUs S results iin larger Co3O(CO O s.61b 2)6 SBUs Also,, Hardie et al reported a rarre example forr framework PSM P invollving direct sitte-specific Cu++ uptake, proceeding in the SCSC trransformation.61c

Dyn namic structu ural transfoormations in nduced by temp perature

Fig.. 11 Scheme view of different tyypes of PSM.

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Activ vation of MOF Fs by heating iis one of the most m familiar ways w to ob btain evacuated d porous sampples. Howeverr, dynamic SC-SC transformation may y occur in thiss process trigg gered by temperature change, c involv ving the bond breakage/form mation and latttice motio on, such as shrrinkage/expannsion, distortion, and sliding..62 Sun et al reportted the thermaally induced heead-to-tail dim merization n for a monon nuclear compoound [Cu(NH3)3(pmsb)](solv vent) (14a,, pmsb = 2,2’-(1,2-phenylennebis(methylene))bis(sulfan nediyl)dib benzoic acid), which can bee dimerized to o form a binucclear

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Che emComm com mplex [Cu2(NH H3)6(pmsb)2](ssolvent) (14b)) via thermal S SC-SC tran nsformation.633a This course also involvess the formationn of a new w Cu–Opmsb bo ond between th he mononucleear motifs, chaanging thee coordination sphere from square-planar s to t square-pyraamidal and d the crystal ccolor from blu ue to green. Th his intra-frameework [2+ +2] dimerizatio on is differentt from that of the solid-statee photo-cchemical [2+2 2] cycloadditio ons of organic molecules. Fuurther, thiss transformatio on can also bee realized by ball b milling m method thro ough the SC-p polycrystal meechanical reacttion. Ovcharennko et al reported r a rev versible topotactic SC-SC reeaction of polyymerizattion-depolymeerization via reepeated coolin ng-heating cyccles.63b In this t transformation, variation of the tempeeratures (295 vvs 225 K) causes consid derable mutuaal displacemen nt of adjacent moleculles, and thus th he trinuclear structure s and 1D 1 polymeric chain isomer can reverrsibly transform m with the coo ordination geoometry of Cu(II) C changin ng from squaree-pyramidal to o octahedral. S Such a stru uctural converrsion is also acccompanied by y magnetic anoomaly cau used by the mo odulation betw ween the odd electron e of Cu22+ and nitrroxide, resultin ng in a reversiible transition from antiferroomagnettic to ferromag gnetic coupling g. Mesbh et al reported a twoo-step deh hydration of [N Ni3(OH)2(tp)2(H ( 2O)4]n (15∙4 4H2O) upon heeating, leading to sequen ntial removal of coordinatio on water to prroduce [Nii3(OH)2(tp)2(H H2O)2]n (15∙2H H2O) at 433 K and [Ni2(OH)2 (tp)]n (15 5) at 483 K.63c Such reversib ble structural transformation t ns will affe fect the magneetic behavior of o each phase, from antiferroomagnettic, to canted aantiferromagneetic, and then to t ferromagnettic. Barbour et all studied a 2-fo old interpenetrrating pillaredd-layer MO OF [Zn2(ndc)2(bpy)]n (16∙2-fold, ndc = naaphthalenedicaarboxylaate), which can n convert to itts triply interpenetrating anaalogue 16∙∙3-fold upon d desolvation by heating.64a With W the aid of single cry ystal diffraction n and computaational method d, the mechaniism of thiss SC-SC coursse was postulaated as that, du uring the conveersion, thee metal-carbox xylate layers sllide laterally with w their connnectivity unchanged, w while the bpy pillars p undergo o Zn−N bond ccleavagee and reformaation. {[Cu(inaa)2(H2O)][Cu(iina)2(bpy)](H2 O)2}n (17 7∙2H2O, ina = isonicotinate)), reported by Kumar et al, sshows two o different 2D D layers, one of which includ des open metaal sites (OM MSs) and funcctional organic sites (FOSs)) (Fig. 13).64b Upon rem moval of waterr guests by heaating, 17∙2H2O undergoes aan SCSC C reaction to prroduce {[Cu(in na)2(H2O)][Cu u(ina)2(bpy)]}n (17), witth the gliding o of the two layeers and expanssion of the efffective voiid and space. R Remarkably, due d to the pressence of both O OMSs and d free FOSs, th his material caan be viewed as a a multifuncctional plaatform to act aas both Lewis acid catalyst and small mo lecule sen nsor for CO2 aand CH3OH, as a well as Lew wis base cataly st and cattion sensor forr Ag+ ion. Add ditionally, it sh hows strong seecondharrmonic generaation/nonlinearr optical activ vity, due to itss noncen ntrosymmetry with large po olarity along th he b axis. Hoou and Battten et al reporrted a (3,18)-cconnected MOF [Co(cpn)(H2 O)2]n (18 8, cpn = 5-(3’--carboxylphen nyl)nicotinate),, which comprrises a relaative smaller h hydrophilic ch hannel constru ucted by conveergent sad ddle-shaped cy ycloclusters [C Co6(COO)6(H2O)12]6+ and cppn2–.64c Thee inert channeel can only be opened upon refluxing in hy hydrated DMF solvent at 160 ºC, to afford a a new hydrated h frameework {[C Co(cpn)(H2O)2](H2O)}n (18∙∙H2O) via an SC-SC S processs with thee crystal color changing from m pink to dark--purple.

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Fig. 13 3 Scheme view off SC-SC transform mation showing th he gliding behavior of 64b the tw wo layers and exp pansion of the efffective void and space. s

Dyn namic structu ural transfoormations in nduced by light Photo ochemical [2+ +2] cycloadditiion reactions are earliest in n the history of solid-state reaction cheemistry.5 The pioneer work and outstanding outcom mes have alreaady been revieewed.18,19,22a Th hus, here we only refer to some interresting examplles in the last two yearss, especially lig ght-induced SC C-SC transforrmations. Lee L and Vittal et e al reported aan SC-SC photto-polymerizaation by [2 2+2] cycloaddition for a 2-fo fold interpenettrating framew work [Zn2(bpeb)(tp)(HC ( OO)2]n (19a, bpeb = 1,4-b bis[2-(4’-pyrid dyl)ethen nyl]benzene) (Fig. 14).65 19aa is photoreacctive owing to the fact that t the infinite ely slip-stackeed conjugated C=C bonds off the bpeb ligands constitute a plane. Photo-dimerizzation of the C=C C bond d pairs in the so olid state is triiggered by UV V light, to afford a new MOF M {[Zn2(po oly-bppcb)(tp))(HCOO)2](H2O)}n (19b, bp ppcb = 1,3 3-(4,4’-bipyrid dyl)-2,4-phenyl ylene-cyclobutaane). For this SCSC dimerization, d th he relative orieentations of bp peb ligands facilitate a close packing of the C=C bonds, and an n organic poly ymer based d on cyclobuta ane rings of ppoly-bppcb is formed. This SCSC photo-polymeri p ization leads tto a structural transformation n of the en ntangled cds network n to a noonentangled jjjv2 framework k.

Fig. 14 4 Scheme view off SC-SC photo-po lymerization by [2+2] [ cycloadditio on with a structural chang ge from 2-fold intterpenetrating to o noninterpenetraat65 ing pattens.

Yang Y and Naum mov et al repoorted the first example e of a regir oseleective SC-SC transformationn via [2+2] ph hoto-dimerizaation in thee pores of CP {[Mn(bpeb)(ppda)](bpeb)}n (20, H2pda = 1,3pheny ylenediacrylic c acid).66 20 reeveals a moleccular reactor comprisin ng a 2D porou us CP with threee photoreactiive sites: the bpeb b guestt and the bpeb b or pda ligandd (Fig. 15). Up pon irradiation n by UV light, l three typ pes of photoreaactions, includ ding the photop polymerrization of bpe eb guests, the photodimerization of bpeb ligands,, and the photo oisomerizationn of pda ligand ds, will be stro ongly coupled togetherr stereochemiccally. The (quaasi)-equilibria for

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ChemCom mm sive phase p 22∙IIb without w aurophhilic interactions. This abnorrmity caan be attributed d to the formaation of multip ple C–H∙∙∙π in nterView Article Online action ns involving the added methhyl groups of10.1039/C4CC06263A 22, which ind duce DOI: the em mergence of th he thermodynaamically stable phase 22∙IIb.

thee three reaction ns (polymerizaation, dimerizaation, and pedaal-like isomerization) caan be considerred as the natu ural consequennce of intrricate and intriinsic structuraal feedback of this t dynamic C CP.

Dy ynamic strucctural transsformations induced by mechanical forcee Thee correlation o on mechanicaal control of so olid-state struuctures and d phase changees in moleculaar crystals has remained relaatively uneexplored. In faact, researchess on anisotropic bulk forces , such as shearing and ball-milling or o grinding, sttimulated struuctural chaanges of the m molecular crysttals have been n proved to be feasiblee, even leading g to SC-SC traasnformations..67 However, aanisotrop pic forces at tthe bulk scale normally breaak the integrityy of a single crystal. Siignificantly, Itto et al reporteed the first exaample of mechanical triiggered SC-SC C transformatiion (Fig. 16).668 The com mpound pheny yl(phenyl isoccyanide)gold(I) (21∙Ib, Ib = polymo orph I in blue ccolor), as the kinetic k polymo orph, can be raapidly isolated and crysttallized from hexane/dichlor h romethane, shoowing thee blue photolum minescence un nder UV irrad diation. In thiss case, eacch molecule fo orms a herring gbone-like patttern with a he ad-totaill arrangement of the phenyl ligands on thee Au(I) centerrs, and theese discrete mo ononuclear mo otifs can be weell isolated wiith the Au u∙∙∙Au distancee longer than 4.65 4 Å, indicaating the absennce of aurrophilic interacctions. Fascinaatingly, when a small pit waas first pro oduced by priccking the fixed d sample with a needle, the phase tran nsformation g gradually spreaads over the entire e crystal aafter 9 hou urs, and a new w thermodynam mically favoreed polymorph 21∙IIy (IIy = polymorph h II in yellow color) c is obtained with the ccrystal collor changing fr from blue to yeellow. Single-ccrystal X-ray aanalysis indicates thatt the molecules of 21∙IIy tak ke a nearly flaat conforrmation, showiing a head-to-ttail arrangemeent with the Auu∙∙∙Au distance of 3.177 7 Å (i.e. the prresence of auro ophilic interacctions). No otably, this meechanical forcee-triggered SC C-SC transform mation resembles domin noes and proceeeds through self-replicationn. And theen, Ito et al furrther introduceed the methyl substituent innto the bassic structure of 21 to afford a green emisssive metastablle polym morph of pheny yl(3,5-dimethy ylphenyl isocy yanide)gold(I) (22∙Ig, Ig = polymorph I in green colo or).69 Remarkab bly, changes ffor the pro ofile of crystall structure and emission enerrgy in SC-SC transforrmation for 22 are opposite to t those observ ved for 21. Nootably, thee crystals of 22 2∙Ig, with interrmolecular aurrophilic interaactions (Au u∙∙∙Au: 3.112– –3.274 Å) willl undergo a piccking-triggereed SCSC C transformatio on to afford th he blue-shifted, weakly blue emis-

10 | Chem. Comm mun., 2014, 50, 1-15

Fig. 16 6 Scheme view off dominoes reacttion through self-replication of SC--SC 68 transfformation triggered by mechanicaal force.

Recently, R Tao et e al reported a new polymo orph for co-cry ystal 7,7,8,8-tetracyanoq quinodimethanne-p-bis(8-hyd droxyquinolinaato) copper(II), which can c show an ooriented SC-SC C phase transiition upon n mechanical stimulation (i.ee. pricked with h a metal need dle). This structural con nversion is acccompanied by y almost doubling its length and halving its thickneess in a macroscopic viewpo oint, which h can be attrib buted to the prrominent chan nges of molecular stack king, with the dihedral d anglees between thee molecular lay yers decreeasing from 55 5.6º to 27.7º, and the a-axis lengths increasing frrom 8.035 Å to 14.098 Å, reespectively.70

Dyn namic structu ural transfoormations in nduced by syynergicc stimuli In some SC-SC transformations, it is necessary y to consider mulm tiple stimuli that may m play a syneergic role in trriggering different solid-state reaction ns. On the one hand, a transfformation requ uires moree than one exte ernal stimuluss to provide ap ppropriate energy, faciliitating the reac ctions and maiintaining the in ntegrity of sin nglecrystallinity. On th he other hand, a given comp pound can be actia vated d by different stimuli s to sufffer dual SC-SC C transformatio ons, and even e multi-step ps reversible trransformation ns. Multtiple stimuli in n one SC-SC transformatiion. Su and Laan et al rep ported an unprrecedented SC C-SC reaction controlled c by both b temperature and tim me in the preseence or absencce of solvent. The transformation from m a 3D noninnterpenetrating g MOF {[(Zn4O)2(tcom m)3](solvent)}n (23a) to a 33D chiral self--penetrating MOF M {[(Zn n4O)2(tcom)3 (H H2O)](solventt)}n (23b), whiich can be view wed as thee kinetic and dynamic d produucts, respectively, will suffer an 7 interm mediate state.71 During this transformatio on, the solventts in 23a move m faster in n channels upoon heating witth a partial breeakage of o the coordina ation bonds, aand different Zn Z 4O(CO2)6 SB BUs movee closer to each h other and aree dimerized by y water molecu ules to forrm [Zn4O(CO2)6](H2O) SBU Us in 23b in a certain time (Fig. 17). Of O further inte erest, 23a dispplays selectivee CO2 uptake over o N2 an nd more excelllent gas sorpti tion ability thaan 23b, while 23b has an a efficient cap pability in reveersible adsorpttion of iodine.

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w of a 2D porous CP C as molecular reactor, r showing three Fig. 15 Scheme view es of photoreactiive reactions: pollymerization, dim merization, and peedaltype 66 like isomerization.

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Fig. 17 SC-SC transfo ormation doubly triggered t by temperature and tim me.

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71

ultiple stimulii in dual SC-S SC transform mations. A 3D MOF Mu {[C Cu(iba)2](H2O))2}n (24∙2H2O, O iba = 4-(1H-imidazol-1-yyl)benzoaate), reported b by Du et al, sh hows a 3-fold interpenetratinng lvt fram mework with the inclusion of lattice watter cubes.72 Innduced by different stimu uli, temperatu ure and time, th his crystalline materiall shows distin nct dual SC-SC C transformations upon rem moving thee lattice water clusters (Fig. 18). As a resu ult, the polymoorphic isomers of 3D po orous framewo ork for 24 and 2D polymericc kgm lay yer for [Cu(ibaa)2] (24b) can be isolated du uring the kinetiic and theermodynamic d dehydrated cou urses, respectiively.

upon n heating, the coordinative c w water ligands and a lattice acettone are both b removed to t give active pores. While left in room temt View Article Online peratture, the coord dinated water m moleculesDOI: are10.1039/C4CC06263A partially replaaced with THF to afford d {[Cd3(btb)2((H2O)(THF)](T THF)}n (26c) and then upon heating, it exhibits a ccompleted repllacement of water w ligan nds by THF to block the actiive pores. Thee dynamic activity of this porous material, as demoonstrated by dual d SC-SC traansformations upon multiple m stimulii, can also be supported s by their t distin nct sorption ca apacities for caarbon dioxide.

Fig. 19 9 Schematic view w showing dual SCC-SC transformatiions to regulate the t 74 chemiical blocking and unblocking of acttive pores.

Fig. 18 Dual kinetic aand thermodynam mic SC-SC transfo ormations upon rremov72 b temperature an nd time. ing lattice water clussters, triggered by

Interestingly,, by simply rep placing the ibaa ligand with 44-(1H1,2 2,4-triazol-1-yll)benzoate (tbaa) in the abovee case, a distinnct 3D MO OF {[Cu(tba)2]](DMF)}n (25·DMF) with th he 4-fold interrpenetratting dia frameework, can be obtained.73 Th he desolvated productt 25 shows excclusive CO2 ad dsorption selecctivity over CH H 4, H 2, O2, Ar, and N2 g gases. Further, [Cu(tba)2]n (2 25) can suffer divergen nt kinetic and tthermodynamic SC-SC hydrration processses, by imm mersing the crrystal in water for minutes or exposing thee crystal to air for seveeral weeks, to o produce its issostructural hyydrate {[C Cu(tba)2](H2O))}n (25·H2O) and [Cu(tba)2(H2O)4] (25b b) as a mo ononuclear com mplex. Such completely c diffferent SC-SC transforrmations of 25 5 first reveal th he duality and sensitivity off MOF maaterials toward d water. Ghosh et al rreported a 3D biporous soft MOF {[Cd1.55(btb)(H2O)](THF)2}n (26a, H3btb = 4,4’,4’’-(benzene-1,3,5-trriyltrimeethylene)triben nzoic acid), wh hich shows thee dual SC-SC transforrmations to reg gulate the chem mical blocking g and unblockking of acttive pores alon ng with guest-d dependent fram mework contraaction and d expansion (F Fig. 19).74 26a a comprises tw wo types of chaannels botth filled with T THF guests, in n which one contains coordiinated water molecules protruding intto the internal voids and thee other is lined l with the hydrophobic surfaces of aro omatic rings aand an eth her-linking mo oiety. This matterial shows tw wo-way moduulation of the t framework k porosity via dual SC-SC trransformationss. The latttice THF in the former pores can be easily y replaced withh aceton ne to form {[C Cd1.5(btb)(H2O))](CH3COCH3)2}n (26b) andd then

Thiss journal is © Th e Royal Society of o Chemistry 201 14

Multtiple stimuli in i reversible SC-SC transsformations. Lee, L Zawo orotko, and Viittal et al repoorted an outstaanding examplle to maniipulate the polymerization annd depolymerization of orgaanic polym mer ligands in n CP via reverssible SC-SC trransformations.75a Yello ow crystals off {[Zn(bpeb)(tpp)](solvent)}n (27a), which has a 6-fo old interpenetrrating dia fram mework, can be b irradiated un nder xenon n lamp at wav velength of 3665 nm for 2 ho ours to afford pale p yellow crystals of {[Zn(poly-bpppcb)(tp)](solv vent)}n (27b) with w a new w (4,4)-connec cted jjv1 net ((Fig. 20). The significant strructural change is maiinly due to thee light-triggereed [2+2] cyclo oaddition n reaction, which can unite tthe six interpeenetrating dia nets n into a single jjv1 ne et. Further, heeating the crystals of 27b to 250 ºC fo or 3 hours in a hot-air oven w will result in th he crystals of 27a. 2 This is the first exa ample involvinng the reversib ble formation and cleav vage of cyclob butane rings inn a CP through h SC-SC transsformatio on. Also, Kawano and Vittall et al reported d another exam mple for reeversible SC-S SC transformaations of cyclo obutane formaation or cleeavage, with regard r to the pphotoreactive ligand trans-4 4,4’stilbeenedicarboxyliic acid.75b Jenk nkins et al repo orted the interresting gate g effect of th he 1D metal-oorganic nanotu ubes in 2D coo ordination frameworks.75c In such an SC-SC transfo ormation triggeered by moisture m or hea ating, the phennyl groups as the t tube walls can rotatee between two o positions to rregulate the sw witch on/off off the poress.

Fig. 20 Reversible SC--SC transformattions from the 6-fold 6 interpenettrat7 75a ing dia framework to single jjv1 net ttriggered by ligh ht and heating.

Che m. Commun., 2014, 2 50, 1-15 | 11

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Tao et al repo orted a unique square FeII4[N N(CN)2]4 comppound, wh hich can show the two-step complete c spin transition viaa guest dessorption/resorp ption-induced SC-SC transfo ormation stimuulated by thermal and o optical irradiatiion.76a Tong an nd Bousseksouu et al fou und the quasi-rreversible tran nsformation beetween the twoo-step spin crossover an nd half spin crossover comp plexes, under moisturee and heating conditions.76b Costa and Arromí et al repoorted a rev versible SC-SC C cycle for [F Fe(bpp)(bmpp))](ClO4)2(C3H 6O)3/2 (28 8a, bpp = 2,6-b bis(pyrazol-3--yl)pyridine, H2bmpp = 2,6--bis(5(2-methoxy-phen nyl)pyrazol-3-yl)pyridine), [Fe(bpp)(bm mpp)](CllO4)2 (CH3COC CH3) (28b), an nd [Fe(bpp)(b bmpp)](ClO4)2 (CH3OH H)5/4(H2O)1/2 (2 28c), via adso orption, desorp ption, and exchhange of small moleculles (Fig. 21).766c Upon heatin ng, 28a transfoormed into o 28b by loss of partial aceetone guests, switching from m lowspin state (LS) to o high-spin statte (HS). Interestingly, such aan SCSC C transformatio on can be reveersed by incorp porating the accetone vap por. Moreoverr, two-step SC C-SC transform mations from 228b to 28cc, and then to 28a can also be b achieved by y providing saaturated methanol and d acetone, with h a magnetic state switchingg from HS S to LS. As a rresult, a reverrsible conversiion cycle is foormed. Sim milar cycling S SC-SC transforrmation triggered by moisturre and heaating was also o observed in the t work by Ma M and Chengg et al, wh hich features an n unusual and controllable metal m ion moveement in the t voids of CP P.76d

7 therm mal elimination n and subsequuent brominatiion (Fig. 22).79 In particcular, 29∙H2O suffers an SC C-SC transform mation to form m the View Article Online guestt-free framewo ork 29 upon hheating toDOI: 12010.1039/C4CC06263A ºC. The hydro oxyethyll tag group (–C CHOHCH3) is free in the chaannel of 29 wh hich can be b modified up pon further heaating to 250 ºC C to give the vinyl v group p (–CH=CH2),, though crystaallinity is lost after this proccess. Such h a PSM metho od affords an uunprecedented d simple moleccule 2-vin nyl-1H-benzo[d]imidazole-55-carboxylic accid, which can nnot be prrepared via tra aditional organnic synthesis. Further, the vinyl v group p can tandemly y undergo an aaddition reactiion with brom mine. Notab bly, the two consecutive PS SMs of eliminaation and brom mination n are realized on o the tag grouup within the highly crystallline solid, which will have drastic efffect on adsorp ption and lumin nescencee properties off the material.

Fig. 22 2 Schematic view w of the tandem PPSM for 29.

79

Con nclusions and d perspectivves

Fig. 21 SC-SC converrsion cycle induceed by heating or vapor. v

76c

Mu ultiple stimuli in tandem structural s tra ansformationss. The CSSs may possess the rigid or flexible naturre at the low orr high tem mperature, resp pectively, and provide the po ossibility of taandem beh haviors in SC--SC transformaation.77 For ex xample, Bramm mer et al reported r a mulltiple SC-SC transformation t n, that is, the nnonporou us CP discardss the lattice sollvent by mild heating h with thhe 1D pollymeric structu ure intact and by further heaating, a 2D CP P with 78a thee crosslinking of organic lig gands will be formed. f Alsso, anoth her tandem SC C-SC transform mation upon deesorption/adsorrption of water w spirals aand coordinateed water by heeating to 323 oor 400 K, was reported by Zang, Son ng, and Mak ett al, which proovides thee first examplee of switchablee ferroelectricc and optical bbehaviors.78b Zeng and Ku urmoo et al rep ported an unussual tandem PS SM of a MOF M {[Zn3(hb bmc)2(OH)2](H H2O)6}n (29∙H2O, H2hbmc = 2-(1hyd droxyethyl)-1H H-benzo[d]imiidazole-5-carb boxylic acid) uusing

12 | Chem. Comm mun., 2014, 50, 1-15

In this article, dyn namic structuraal transformattions of coord dinaar systems trigggered by diffferent exogen nous tion supramolecula uli have been illustrated. i Wit ith regard to th he object of stu udy, stimu somee crystalline re eactive charactteristics, inclu uding metal no odes with adjustable electronic configgurations or co oordination geometriess, ligand linkers with active functional gro oups, framewo orks with flexibility for twisting, and special voids for guest capture or reaaction, are of the necessity. More importaantly, the delicate selection of the piv votal factors, ssuch as concen ntration, temperature, light, mechanical force, as w well as their sy ynergic influen nce, b key to achieve the proposeed structural trransformation.. On will be one hand, h upon exogenous stimuuli, the metal nodes will und dergo th he change of co oordination geeometries, inseertion of additiional meetal nodes, red dox reaction, oor exchange off metal nodes. On the other hand, org ganic linkers caan also suffer appropriate traansformations, such ass ligand exchaange, ligand peedal isomerizaation, nd modification n, or ligand ppolymerization n. As a result, the ligan host frameworks will w show diverrse functionaliity as guest ad dsorbentss or molecular reactors, and network flexib bility in breath hing phenomenon, entan nglement, and repacking arrangement.

This T journal is © The Royal Society of Chemistry 2014 2

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ChemComm Benefiting from the advantages of single-crystal X-ray diffraction and other analysis techniques, there is an obscure borderline between single-crystallinity and poly-crystallinity. Thus, a solid-state reaction may be remarkably monitored as a whole story from alpha to omega. More fascinatingly, some coordination supramolecular systems, which may only be obtained from dynamic structural transformations, will have peculiar physicochemical properties in adsorption, magnetism, luminescent, and catalysis, revealing proof-of-concept for applications in the rational design of new functional crystalline materials.

Feature ARTICLE 2012, 11, 710–716; (b) R. Q. Zou, H. Sakurai, S. Han, R. Q. Zhong and Q. Xu, J. Am. Chem. Soc., 2007, 129, 8402–8403; (c) D. Tanaka, View Article Online

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We are grateful to the National Natural Science Foundation of China (Nos. 21031002, 91122005, and 21101116), Program for Innovative Research Team in University of Tianjin (No. TD125038), and Plan for Scientific Innovation Talent of Henan Province for financial support.

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Photogra aphs and d Brief Bio ographies s

Jiing Chen was born in 1986, China. She ob btained her BS S in 2008 and M MS in 2011 fro om Tianjin N Normal Universsity under the supervision off Prof. Miao Du. D Then, she jjoined the facu ulty at Tianjin N Normal Universsity and her cuurrent researcch focuses on crystal c engineeering of coord dination polym mers.

Chun-Sen Liu was born in Z Zhengzhou, Ch hina. He obtain ned his BS in 11997 from Tianjin Normal University, an nd his PhD in 22007 from Nan nkai University y under the sup upervision of Prof. P Xian-He B And then, he joined the ffaculty at Zhen Bu. ngzhou Univerrsity of Light IIndustry, wherre he is now a P Professor of Chemistry. C Hiss recent researrch interest foc cuses on metall-organic fram meworks (MOFs) for po otential appliccations.

Miao Du was born in Kaifenng, Henan Pro M ovince, China (1976). He recceived his BS from f Nankai University (19 998), and subseequently his doctorate d there e (2003) underr the supervisio on of Prof. X Xian-He Bu. Then, T he joinedd the faculty at Tianjin Norm mal Universityy and now is a Professor of Chemistry. Hee has worked w with Prof. Thomas C. W. Ma ak at the Chineese University of Hong K Kong and Dr Qiang Q Xu at thhe Institute of Advanced A Ind dustrial Sciencee and Technollogy of Japan (JSPS fellow). His current rresearch lies in n coordination n chemistry andd crystal engin neering.

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Cheng-Peng Li was born in 11981, in Linfen C n, Shanxi Province, China. H He received hiss BS in 2003 an nd MS in 2006 6 from Tianjin Normal Univeersity, and his PhD in 2009 ffrom Tianjin University. U C Currently, he iss an associate pprofessor at Tianjin T Normall University annd focuses on coordination su upramolecularr systems and ttheir propertiees, especially dynamic d struct ctural transform mations.

Dynamic structural transformations of coordination supramolecular systems upon exogenous stimulation.

Reactions in the solid state, especially single-crystal-to-single-crystal (SC-SC) transformations, provide an appealing pathway to obtain target cryst...
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