多孔配位聚合物合成、结构以及性质研究

汕头大2013多孔配位聚合物的合成、结构以及性质研究Synthesis,StructuresandPropertiesofPorousCoordinationPolymers 梁玮 师 教答辩（签名:答辩日期：2013635-（3-甲基-5-吡啶-1,2,4-三氮唑）间苯二甲酸（H2L）在溶剂热条件下结构新颖的多酸类配体的研究现状，并阐述本的研究目的和意义。第二章主要研究了在温度和溶剂的共同调控下，合成得到了一对超分子异构体[Cd(L)(H2O)]∙THF∙2H2O1)、[Cd(L)(H2O)]∙3H2O2)，其主要是三氮唑上参与配位的氮原能通过除去苯甲醇提纯苯。Zn(II)配合物[Zn2(L)2]·7.5H2O58%的多孔结构，而且其大孔四周填充有甲基，形成了憎水的环境。同时还对配合1D2D3D维多孔结构的转变，从无孔到多孔的转变。在不同溶剂调控下将配体与硝酸铜反应，得到三个具有新颖结构的配位聚合物[Cu(HL)](4)[Cu(HL)]·2O(5)、[CuL]·nH2O(6)Coordinationcomplexespossesspotentialapplicationsingasstorage,adsorptionbasedgas/vaporseparation,shape/size-selectivecatalysis,drugstorageanddelivery,optical,electricalandmagnetismproperties.Multifunctionalligandscontainingcarboxylicgroupsandnitrogenatomsasdonorshavebeenwidelyusedtoarchitectvarioustypesofcoordinationpolymers.Sowemainlyinvestigatetheconstructionofthenovelandmultifunctionalcomplexesbasedon5-(3-methyl-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-yl)isophthalate(H2L)undersolvothermalreactioncondition.Thisthesisisdividedintofivechapters.Inchapter1,thesynthesisanduseofporouscoordinationpolymers(PCPs)aremainlysummarized.Thehistoryandactualityofsomenotablecompoundsbasedonligandscontainingcarboxylicandnitrogendonorsarebrieflyreviewed.Inaddition,theintentionandsignificanceofcoordinationpolymersbasedonmultifunctionolligandsarealsoelucidated.Inchapter2,transitionmetalionsCdII),H2Lligandhaveself-assembledresultinginapairofsupramolecularisomersCd(L)(H2O)]∙THF∙2H2O1)[Cd(L)(H2O)]∙3H2O2)，whichcouldbecontrolledandregulatedthroughasolventandtemperaturesimultaneouslytuningstrategy.1isarare2Dbipillar-bilayerstructureand2isa3Dstructure.Interestingly,1and2displayeddifferentseparationperformancebasedonuniquepropertiesoftheirpores:2couldseparatebenzylalcoholfromphenol,and1couldnotonlypurifybenzaldehydebyabsorbingbenzylalcoholbutalsoseparatebenzylalcoholfromphenol.Inchapter3,wereportthesynthesesofanovelcoordinationcomplexe:[Zn2(L)2]·7.5H(3)byreactionoftransitionmetalionswithH2Lundersolvothermalreactionconditions.Compound3isarare3DPCPswiththreediffererntspores,possessingahydrophobicmacroporous.Eachligandanionisbondedwithfourmetalcationsaftercompleydeprotonationwithpyridinegroupandcarboxylgroupalmostlyina90°.Inchapter4,effectsofreactionconditions,suchaspH,solvent,counteranion,temptationonfinalstructurearediscussed.Byregulatingsolvent,wegetthreecompounds,[Cu(HL4)、[Cu(HL)]·H2O5)、[CuL]·nH2O6realizingchangefrom1Dto2Dthento3D.[Co(HL)(OH)(H2O)2]·H2O(7)、[Co4(L)4]·NMP·EtOH·nH2O(8)areobtainedbyregulatingreactiontime,andreachingthransformfromnonporoustomicroporous.Finally,themainachievementsandconclusionsinthisthesisaresummarized.Thefurtherresearchplaninthisprojecthasalsobeenproposed.Keyword:Multifuctionalligands;regulation;porouscomplexes;adsorption;............................................................................................................................................I 第一章绪 参考文 第二章镉配合物的合成、结构与吸附性质研 引 26 配合物1-2结构分 配合物1-2合成分 小 参考文 第三章锌配合物的合成、结构与荧光性质研 引 47 小 参考文 第四章铜/钴配合物的合成、结构与合成研 引 57 小 参考文 第五章结 附录2：部分配合物1~8的红外光谱 攻读期间和拟的................................................................................致 个人简 节。通过改变金属离子的种类、有机配体的种类、pH值、溶剂，温度、压力等均有可调机骨架（Metal-OrganicFrameworks,MOFs）或者无机-有机杂化材料（Inorganic-OrganicHybridMaterials。域表现出了前景[13-18]。多孔金属有机框架是通过金属离子或者金属簇和有机配体自组装而成。不像经典的沸石（硅酸铝）Al3+/Si4+O2-/OH-来构筑结构，多孔金属温度、溶剂、pH值、压力等各种外部条件来调节多孔金属有机框架的结构和性能[19-26]。实[27-29]2001年通过引入溶剂热法得到了多孔的MOF-14,这也为制造多孔的金属有机框架极偶极作用力，π-π作用力等，使其在吸附，催化，分子识别方面有着很好的应用前景。多孔金属有机配位聚合物的合的金属离子主要为二价过渡金属离子如Zn2+、Cu2+、Ni2+、Co2+等。我们知道金属离子配位模式多样化：如Cu2+有四、五、六配位，最常见的是六配位，Cu+一般是二、三、四配选用适宜的模板试剂可以得到具有理想孔洞的结构[32-35]1-1表示了模板剂的作用[36][37-44]。因此就需要在调控MOF的网络拓扑结构时，需综合考虑金属离子、有机配体及其1-1多孔金属有机框架的稳MOFMOF的稳定性是其应用于其他方面的1-2所示的(3,24)-拓扑[45-46]，尽管配体Figure1-2Frameworktopologya)cuboctahedraasstructuralbuildingunits;b)(3,24)-connectednetwork;c)3DpolyhedrapackingSBU（二级结构单元）1-3a4,4-联吡啶虽然得到了许多结构，但是当通过延长配体来得到大孔的结1-3b中，通构[49-50]medEddaoudi等人详细介绍了二级结构单元在构造稳定的多孔金属有机框架SBU作为一个刚性的顶点，可以通过有机配体连接形成高度稳定的结构，通过引入SBU，可以获得稳定的多孔结构[51]。Figure1-3EffectofSBUofporouscoordination多孔配位聚合物的应多孔金属有机框架在催化、分离、吸附、气体、光学材料等领域有着很好的应现为解决氢气的提供了一个方法[52-56]。多孔的有机金属框架和氢气之间有着很强的作加气体吸附的位点。为了增加孔洞和气体的作用力，近年来，在结构中引入了不饱和金属位点来增加框架和气体的作用，以达到增大气体与吸收的能力获得了很大的成功。1-4所示，通过改变金属离子以及阴离子来研究金属中心的电荷密度与氢气吸附的关Figure1-4ImpactofmetalandanionsubstitutionsonthehydrogenstoragepropertiesofM-BTTmetal-organicframeworks统的分离，通过多孔MOF进行分离，可以在常温条件下进行，因而使有机物避免降性的匹配度，特别是主体框架与被吸附分离物质之间的作用力：氢键、π-π作用，以及偶有害的阴离子。HiroshiKitagawa用同时具有氢键供体和受点的金属有机配合物，利用Figure1-5Hydroxylgrouprecognitionbyhydrogen-bondingdonorandacceptorsitesembeddedinalayeredmetal-organicframework多孔有机金属框架在传感方面也应用比较多[65-71]，传感主要基于MOF接触到被分离化合物都会使荧光猝灭。近来，Ghosh等人甚至可以高选择性的对TNP（苯）有感MOF，当把其浸泡在各种溶剂中（乙腈，水，三氯甲烷，乙醇，甲醇，，可以实现客体分子的交换，并且随着客体分子极性Figure1-6Solvatochromicbehaviorofametal-organicframeworkforsensingsmallMOF在气体吸附，有机小分子分离，对小分子的感应方面的选题意在配位聚合物中，金属离子作为电子接受体，而配体中的N、O、S、P等杂原子作引入第二配体，构筑了非常多有意思的结构，紧接着利用加长版的4,4-联吡啶来构筑MOF更是层出不穷。pH值，温度等调控，可以调节羧基去质子的数目，羧基可以单齿配位或1-7SBU结构单元1)双核明轮；2)三核沙漏；3)三核棱镜；4)四核立方；5)Figure1-7Commonencounteredsecondarybuildingunits(SBU):1)dinuclearpaddlewheel;2)trinuclearhourglass;3)trinuclearprism;4)tetranuclearcuboid;5)tetranuclearoctahedronSusumuKitagawa等人在2010年的Angew杂志上了一篇文章[80]，运用羧酸类的配Figure1-9ControlofinterpenetrationbyasolventtuningRolandA.等人同样运用混配，将修饰过的羧基类配体（在苯环上接一个烷基醚取陈小明、张献明等人在2007年，用5-羧基苯并三氮唑与硝酸钴反应，得到了一例具1l·3.7H2O则1-10Co3(OH)2(btca)2]·3.7H2Oa)配位环境图和b3D的极大[84-87]。如今，已有许多具有螺旋结构、手性、和特殊拓扑的化合物被合成和报Kitagawa研究组，的Eddaoudi研究组，以及中国福建物构所的杨国昱研究组及中山大学的鲁统部研究组课题组等在这个领域做出了很多优秀的工作。如图1-12所示，Eddaoudi课题组使用咪唑二羧酸，得到了一系列有趣的的多孔配合物，这些配合物在吸Figure1-12SchematicDrawingoftwocompoundsbasedonimidazole-2-carboxylic90。陈小明课题组使用此配体与锰盐、钴盐反应，得到了一系列的配合物8889]，并对他们的磁。属配位聚合物，他们具有良好的发光、催化性能。2009年，课题组使用吡啶二羧酸配体(H2pdc)与Eu3+离子反应，得到了一个三维多孔结构，此外吡啶上露的氮原子，可以作为感应金属离子的荧光材料[92]（图1-13。图1-13a)配合物[Eu(pdc)15(DMF)]·(DMF05(H2O)05的三维结构图；b)将去溶剂分子后的配合物浸泡在Figure1-13a)3Dstructureof[Eu(pdc)15(DMF)]·(DMF)05(H2O)05;b)Theexcitation(┅)andPLspectra(━)of[Eu(pdc)15(DMF)]activatedinDMFsolutionsofCu(NO3)2atdifferentconcentrations比较有利于得到各种金属簇和稳定的SBU，再通过吡啶类的配体将其延伸出去，从而得结构[93]2012年利用此配体得到了六个配合物，而且其中三个配合物可以进行转换，这主要得益于配体中三氮唑以及苯羧酸的重排[94]2012年，他们将单羧酸换成二羧酸得到了具有twf-d拓扑的10个多孔MOFs,孔洞率达到了66%，通过对配体上取代Figure1-14Anisomorphousseriesofcubic,copper-basedtriazolylisophthalate配合物尤其是在构筑MOFs方面也引起了越来越多的关注。其次羧酸类的配体可以单齿1.2.2主要进1[Cd(L)(H2O)]∙THF∙2H2O1)、[Cd(L)(H2O)]∙3H2O(2)1是比较少见的双层双配合物2能分离共沸物苯酚和苯而配合物1不仅能分离共沸物苯酚和苯而且还能通过吸收苯甲醇提纯苯。常少见的三维三孔的孔洞率达58%的多孔结构，而且其大孔四周填充有甲基，形成了憎[Cu(HL4)、[Cu(HL·2O5)、[CuL]·nH2O6)的调节，得到两个配位聚合物[CoHL)(OH)(H2O)2]·H2O7)、[Co4(L)4]·NMP·EtOH·nH2O游效曾，我国配位化学进展，化学通报，1999,(10),7-Huang,C.-H.(黄春辉);Li,F.-Y.();Huang,Y.-Y.(黄岩宜),UltrathinFilmforOpticsandElectronics(光电功能超薄膜),BeiJingUniversityPress(),洪茂椿，陈荣，梁文平，21世纪的无机化学，科学Cohen,S.M.,Postsyntheticmethodsforthefunctionalizationofmetal-organicChem.Rev.,2012,112,970-Cui,Y.;Yue,Y.;Qian,G.;Chen,B.,Luminescentfunctionalmetal-organicChem.Rev.,2012,112(2),1126-Gagnon,K.J.;Perry,H.P.;Clearfield,A.,Conventionalandunconventionalmetal-organicframeworksbasedonphosphonateligands:MOFsandUMOFs.Chem.Rev.,2012,112,Getman,R.B.;Bae,Y.S.;Wilmer,C.E.;Snurr,R.Q.,Reviewandysisofmolecularsimulationsofmethane,hydrogen,andacetylenestorageinmetal-organicframeworks.Chem.Rev.,2012,112,703-723.Horcajada,P.;Gref,R.;Baati,T.;Allan,P.K.;Maurin,G.;Couvreur,P.;Ferey,G.;Morris,R.E.;Serre,C.,Metal-organicframeworksinbiomedicine.Chem.Rev.,2012,112,Kreno,L.E.;Leong,K.;Farha,O.K.;Allendorf,M.;VanDuyne,R.P.;Hupp,J.T.,Metal-organicframeworkmaterialsaschemicalsensors.Chemicalreviews,2012,112,Li,J.R.;Sculley,J.;Zhou,H.C.,Metal-organicframeworksforseparations.Chem.2012,112,869-Suh,M.P.;Park,H.J.;Prasad,T.K.;Lim,D.W.,Hydrogenstorageinmetal-organicframeworks.Chem.Rev.,2012,112,782-835.Wu,H.;Gong,Q.;Olson,D.H.;Li,J.,Commensurateadsorptionofhydrocarbonsandalcoholsinmicroporousmetalorganicframeworks.Chem.Rev.,2012,112,836-868.Maes,M.;Trekels,M.;Boulhout,M.;Schouteden,S.;Vermoore,F.;Alaerts,Heurtaux,D.;Seo,Y.K.;Hwang,Y.K.;Chang,J.S.;Beurroies,I.;Denoyel,R.;Temst,K.;Vantomme,A.;Horcajada,P.;Serre,C.;DeVos,D.E.,SelectiveremovalofN-heterocyclicaromaticcontaminantsfromfuelsbylewisacidicmetal-organicframeworks.Angew.Chem.Int.Ed.,2011,50(18),4210-4214.Fei,H.H.;Rogow,D.L.;Oliver,S.R.J.,Reversibl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