Synthesis, Crystal Structure, and Luminescence of Cadmium(II) and Silver(I) Coordination Polymers Based on 1,3-Bis(1,2,4-triazol-1-yl)adamantane.

Roman D Marchenko,Taisiya S Sukhikh,Andrei S Potapov,Alexey A Ryadun

doi:10.3390/molecules26175400

Abstract

Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO3]n, in which metal ions are linked by 1,3-bis(1,2,4-triazol-1-yl)adamantane ligands, coordinated by nitrogen atoms at positions 2 and 4 of 1,2,4-triazole rings. Layers of the coordination polymer consist of rare 18- and 30-membered {Ag2L2} and {Ag4L4} metallocycles. Cadmium(II) nitrate formed two kinds of one-dimensional coordination polymers depending on the metal-to-ligand ratio used in the synthesis. Coordination polymer [Cd(L)2(NO3)2]n was obtained in case of a 1:2 M:L ratio, while for M:L = 2:1 product {[Cd(L)(NO3)2(CH3OH)]·0.5CH3OH}n was isolated. All coordination polymers demonstrated ligand-centered emission near 450 nm upon excitation at 370 nm.

Highlights

Since its discovery adamantane has gained a wide spectrum of applications—from polymer design to biological activity
Natural and synthetic adamantanes possess a wide range of biological activity
Derivatives of 1,2,4-triazole are known as anticancer, antiproliferative, anti-inflammatory, anticonvulsant, analgesic, antioxidant agents, and possess activity against wide, but specific spectrum of living organisms [10]. 1,2,4-Triazole cycles and rigid adamantane structures can be combined in bis(1,2,4-triazolyl)

Summary

Introduction

Since its discovery adamantane has gained a wide spectrum of applications—from polymer design to biological activity. 1,2,4-Triazole cycles and rigid adamantane structures can be combined in bis(1,2,4-triazolyl). 1,2,4-Triazole cycles and rigid adamantane structures can be combined in bis(1,2,4zolyl)adamantane ligands, which could be useful N,N’-linkers for cons2trouf c1t0ing coord tion polymers. Coordination polymers and metal-organic frameworks in particular promising materials with a wide range of potential applications—gas storage and sep tion [11,12], enantioselective catalysis [13,14], supramolecular systems design [15], p adamantane ligatanndtss, ewnhsinchg c[1o6u,l1d7]b,ewuasteefrupl uNr,iNfi’c-alitniokner[s18fo],rfcaobnrisctaruticotninogf ceoleocrtdroincahteiomnicpaolldye-vices [19 mers. Atom o cCadti(oIIn)scaarteiLolnimnskoaerldeecbliuynlkbeeraiddngbdiynabgnrLidomgxioynlggeecLunlmeastooilnemtcouo1lefDsacinhctaooion1rsDd{iCcnhdaa(tNiendOs 3{m)C2(deLt()hN(CaOnH3o)3lO2(mLH)o)(}CloeHrciu3eOlnetH.edB)}oth of t ac(Åt(poCto22illraoo,oH..i6a6rFnsenab99·enig·lg594p·tlcOueecÅ(lÅold2rarny)ce.tn,6aolstoFe6o9itcacaltroioha)a9alscl(g.boonbFneltetuTÅlsiseginposcogrhset)gbolgewchunceaorenrcos6nroscayertteeo)owerrpeasa.bnytctnSrchr(TeeeaodtsFt8eiettlsshantc)wilihntalg.ocnebtaiealetgusaneatxlsceemrnhrottkitanweesecsdgbeepdoSbtejretdnhohnth8eat(hitiiew)ntbaFpctno.aerniymhactagetoehlhtxtieubeoslaeceientrrsmncjheaniocihbgdoahtxoii6nhtnne(gailo)rFesssoe.iaitfinctnTlhtgbauesnimNgehunn(liiieerFcdntdLoo–esrhictlnOeageom1a6ahspct,un)ias2en.udaeoduir,Tsnnln4lieipeseths-doidshrttnc6enraaaeea1u)tirmnsocn.an,1le2hzTecdt,osa,2iaoe4suhnCln,it-lse4niphveetdncd-rsoerouticht(arafla1o1IlhvimyazrIa2,,aee2d)12orz.odi,3D,rl2iio4nl4enoo3eD-lis-egvtnnch0ctrueolhra(yhsiiaa7nillnrdayayvacz)etidrzreeaaoenoÅidrrotnrl2nsgoseomlDiemvageo{bnhConneroelyshliiandldnaeedyvcyacntta(roeot2eeduNottrrnmoed.lgprs6madOmsoeo0sroiinognps3d2sraC)lieia(aett2(eieH7ni(r2cntrponLao).ue·t6notl·ma)elÅdel·9s(aOetrd54Cisrolm-a(mHTsoa3bslObeiadclHetue)nSlp (2.699 Å ) or between the methanol molecules and the 1,2,4-triazole hydrogen ato Å , Figure 6). These contacts join the chains into supramolecular 2D layers oriente to ab plane (Figure S8). Tahnede4x1c0itantmionaassnodcieamteidsswiointhspπe–cπtr*a troafntshietiofrneseilnig1a,2n,d4-ctroinaztaoilne arinsignsg[l3e6b] a(nFidgunreear7a3)5.0Tnhme eaxncidta4ti1o0nnamndasesmoicsisaitoend swpeitchtrπa–oπf* thtreancsoiotirodnisnaintio1,n2,p4-otlryiamzoerles r1i–n3gsar[e36v]e(rFyigsuimreil7aar),. cTohnesiesxtceintattwiointhanthdeeimntirsasliiognasnpdecntartauorfetohfe thcoeolrudminianteisocnenpcoel.yImnecrosn1t–r3asatrteovtehreysspimecitlraur,mcoonfstihsteenfrtewe iltihgatnhde iLn,trtawliogaenxdcitnaatitounreboafntdhse wluemreindeesteccetnecde.inInthceonsptreacsttrtaootfhtehsepceocotrrudminaotfiotnhepforleyemliegrasn1d–3L,(Ftwigoureexc7ibta,ct)i,otnhebalonwdserweenr-e edrgeytecbtaenddindethmeosnpsetrcatrtaesoaf tbhaethcoocohrdroinmaitciosnhipftoltyom37e0rsn1m–3r(eFliagtiuvreely7bto,c)t,htehefrleoewliegraennde,rigny abdadnidtiodne,mhoignhst-reanteersgaybbaathnodcsharopmpeicarshaitft27to0 3n7m0 ,namssroecliaattivedelywtioththne–πfr*eetrlaignasnitdio, nins aindd1i,t2i,o4n- , trhiiagzho-leenreinrggys.bTahnedesmaipspsieoanr baatn2d70alnsomu, nadsseorcgioaetesda wbaitthhonch–πro*mtriacnsshiitfitonofs 4in0 n1m,2,4u-ptroinazeoxl-e criitnatgios.nTahte37e0mnismsi.oEnxbciatnatdioanlsaot u27n0denrmgoleesadasbtaoththoecharpopmeaicrasnhcieftooffa4h0ingmheru-penoenregxycsithaotuiolndaetr3n7e0arn4m00. nEmxc,iptarotiboanbalyt a2s7s0ocnimateldeawdisthtothtehπe*a–pnpeemarisasniocen pofatahwhiagyh(eFri-geunreerg7yb)s.hSoimulidlaerr pnheoatrop40h0ysnimca,l pbreohbaavbiolyr wasassocoibasteerdvweditphrtehveioπu*s–lny feomr icsasdiomniupmathcwomaypl(eFxigesurwei7thb)s.trSuimctuilra-r apllhyostoimphilyasri1ca-(l1b,2e,h4a-tvriioarzwola-1s-oybl)saedrvamedapnrtaevnieo[u3s2ly]. for cadmium complexes with structurally similar 1-(1,2,4-triazol-1-yl)adamantane [32]

Materials and Methods

Characterization Methods

X-ray Structure Determination

Conclusions