Synthesis, Crystal Structures And Properties Of Coordination Polymers With Flexible Polydentate Azoly Ligands

Coordination polymers have potential applications in gas storage, separation,microelectronics, photoluminescence, magnetism and catalysis. We design andsynthesize36new functional coordination polymers with flexible polydentate azolyligands in this thesis, and discuss influence on the self-assembly of the flexible ligandwith metal atoms to construct coordination architectures with different structures. Themagnetic properties, photoluminescent properties and thermal stability of them havebeen studied. We investigate how to control the structures and properties of desiredcoordination polymers. The progress of this thesis is briefly introduced as follows.1. The assembly reaction of1,4-bis（1,2,4-triazol-1-yl）butane with different Cu（Ⅱ）salts, and aromatic polycarboxylate co-ligands,1,2-benzenedicarboxylate and1,2,4,5-benzenetetracarboxylate yields a series of coordinationpolymers[Cu（btb）（HCOO）₂（H₂O）₂]_n（1），[Cu（btb）₂Cl₂]_n（2），[Cu（btb）（NCS）₂]_n（3），{[Cu（btb）₂（H₂O）₂]（ClO₄）₂}_n（4），{[Cu（btb）₂（H₂O）₂]（NO₃）₂}_n（5），[Cu（btb）（1,2-bdc）]_n（6）and {[Cu₂（btb）（btec）（H₂O）₃]·0.5H₂O·CH₃OH]_n（7）. The results demonstrate that thenature of counteranions or/and aromatic polycarboxylate co-ligands have a remarkableinfluence on the self-assembly of the flexible ligand with metal atoms and constructcoordination architectures with different structures. The magnetic properties ofcoordination polymers3,6,7were studied.2. Three ‘‘pesudo’’ supramolecular isomers were obtained by the slow diffusionmethod using different solvent systems with the same proportion of btb and Mn（SCN）₂.[2D-Mn（btb）₂（NCS）₂][1D-Mn（btb）₂（NCS）₂]（10） is （1D+2D/3D） polycatenated array,composed of two supramolecular isomers [Mn（btb）₂NCS)₂]（CH₂Cl₂）（8）（2D （4,4）network） and [Mn（btb）₂（NCS）₂]（CH₃NO₂）₂（9）（1D ribbons of rings）. The fascinatingpolycatenated topology observed of10is novel. Moreover, we obtain the twopolycatenated motifs are supramolecular isomers of8（simply2D （4,4） network）and9（simply1D ribbons of rings）. 3. Three Mn（Ⅱ） coordination polymers {[Mn（bte）（NO₂-1,3-bdc）（H₂O）]·H₂O}_n（11）,{[Mn（btp）（NO₂-1,3-bdc）（H₂O）]·2H₂O}_n（12） and {[Mn（btb）（NO₂-1,3-bdc）-（H₂O）]·H₂O}_n（13） were synthesized by the combination of the different spacer lengthsand conformational felxibilities ligands bte, btp, btb and rigid NO₂-1,3-bdc.11is agood example that two chains connect the ring subunits and form the independent1DMONT.13is the first independent1D MONT constructed by three chains.11and13are the first example of the polythreaded arrays of the independent1D MONTs. Thephotoluminescent properties of them were studied.4. We have successfully synthetized a series of1D,2D, and3D metal-organiccoordination polymers {[Zn（bte）（1,3-bdc）]·H₂O}_n（14）,{[Zn（bte）（5-NO₂-bdc）]·3H₂O}_n（15）,{[Zn（bte）₂（H₂O）₂]（HSIP）·4H₂O}_n（16）,{[Zn（bte）（cis-chdc）]·H₂O}_n（17）,{[Zn（bte）（fum）]·3H₂O}_n（18）,{[Zn（bte）（Hbtc）]·3H₂O}_n（19）,{[Zn₃（bte）₂（btc）₂（H₂O）₂]·H₂O}_n（20）,{[Zn2（bte）（btec）（H₂O）4]·2H₂O}_n（21）,{[Zn（btb）（cis-chdc）]}_n（22）,{[Zn（btb）（cis-fum）]}_n（23）,{[Zn（btb）（fum）（H₂O）₂]}_n（24） and {[Cd（btb）（fum）（H₂O）]}_n（25） based on different polycarboxylate anions, flexible ligands and d10. The structuraldifferences show that the ligand and the metal center have great influences on thestructure of the final assembly. The photoluminescent properties of them were studied.5. Five iron（Ⅱ） coordination polymers [Fe（bte）₂（NCS）₂][Fe（bte）（H₂O）₂（NCS）₂]}_n（26）,[Fe（bime）（NCS）₂]_n（27）,[Fe（bime）（dca）₂]_n（28）,[Fe（bime）₂（N3）₂]_n（29） and[Fe（btb）₂（NCS）₂]_n（30） with three kinds topologies were synthesized by the slowdiffusion method in H₂O/EtOH medium using the flexible azoly ligands. Thecoordination anions （NCS-, dca and N3-） and the structural characteristics of the flexibleligands play an important role in the assembly of the topologies. The magneticproperties of them were studied.6. We hydrothermally synthesized two novel copper（Ⅱ） complex [Cu4（μ3-OH）₂-（SIP）₂（H₂O）₂]_n（31） and [Cu5（μ3-OH）₂（phth）4]（32） containing a multinuclear copper（Ⅱ）cluster with two flexible azoly ligands and polycarboxylate ligands.32is the firsttwo-dimensional network based on a pentanuclear copper（Ⅱ） cluster, and showsdominant ferromagnetic interactions within the pentanuclear cluster.7. A2D copper coordination polymer {[Cu（abit）（NO₃）]·5H₂O}_n（33） wassynthesized by reaction of Cu（NO₃）₂and abit in a CH₃OH/H₂O medium. It contained anovel T4（1）6（1） water tape consisting of chair-shaped water hexamer with two danglingwater molecules and uudd configuration of tetramer water. To the best of our best knowledge, no T4（1）6（1） water tape has been structurally analysed up to now.8. Three polythreaded Co（Ⅱ） coordination polymers [Co（obtz）（NO₂-1,3-bdc）]_n（34）、[Co（mbtz）（NO₂-1,3-bdc）（CH₃OH）]_n（35） and [Co（bbtz）（NO₂-1,3-bdc）（H₂O）]_n（36）were synthesized by the combination of three position isomers obtz, mbtz, bbtz andrigid NO₂-1,3-bdc.34is an unprecedented polythreaded framework. It is the first2D3D polythreaded framework based on the polycatenated2D layers.