冠醚及其類似物：穴狀配體，開鏈配體和球狀配體的主-客體化學(xué)Host-guestchemistryofcrownethers(coronands),podands,cryptands,andspherandsHostorreceptor:crownether,etc.…Guestorsubstrate:metalion,etc.…冠醚及其類似物：穴狀配體，開鏈配體和球狀配體的主-客體化學(xué)11.冠醚的發(fā)現(xiàn)1967，C.J.Pedersen偶然獲得,(1987Nobel獎)1.冠醚的發(fā)現(xiàn)2KMnO4+冠醚溶于苯或氯仿—K+離子掉進(jìn)了冠醚分子的洞中：由此開創(chuàng)了冠醚類化合物、主-客體化學(xué)、分子識別的研究乃至開創(chuàng)了超分子化學(xué)。KMnO4+冠醚溶于苯或氯仿—由此開創(chuàng)了3Valinomycin(left)givesastrongandselectivecomplex(right)inwhichaK+ionisincludedinthemacrocycliccavity.Valinomycin(left)givesastr42.冠醚類化合物的種類和結(jié)構(gòu)2.冠醚類化合物的種類和結(jié)構(gòu)5冠醚（crownethers，單環(huán)體系）冠醚（crownethers，單環(huán)體系）6主客體化學(xué)newppt課件7主客體化學(xué)newppt課件8主客體化學(xué)newppt課件9主客體化學(xué)newppt課件10穴狀配體（cryptands，多環(huán)體系）由J.M.Lehn引入1987Nobel獎穴狀配體（cryptands，多環(huán)體系）11開鏈配體（podands）開鏈配體（podands）12其他“組合”配體：octopus&lariatethers其他“組合”配體：13其他“組合”配體：spherands（Cram引入，1987Nobel獎）

其他“組合”配體：spherands（Cram引入，1914(c)cylindricalmacrotricylic(d)sphericalmacrotricylic(a)macrocyclic(b)macrobicyclic(c)cylindricalmacrotricylic153.冠醚類化合物的性質(zhì)和分子識別冠醚的兩親性(親脂性和親水性)和溶解性：不同的溶劑中構(gòu)象不同3.冠醚類化合物的性質(zhì)和分子識別冠醚的兩親性(親脂性和親水16配合物在非極性溶劑中更穩(wěn)定配合物在非極性溶劑中更穩(wěn)定17冠醚對堿金屬陽離子的配合—球形識別(SphericalRecognition)

冠醚環(huán)大小的選擇效應(yīng)冠醚對堿金屬陽離子的配合—球形識別(SphericalRe18環(huán)過大時能容納兩個陽離子環(huán)過大時能容納兩個陽離子19對過渡金屬的配合—配位原子的變化—N或S替代O，改變配位行為（HSAB理論）對過渡金屬的配合—配位原子的變化—N或S替代O，改20配體的拓?fù)湫?yīng)配體的拓?fù)湫?yīng)21配合物形成速度（動力學(xué)）：穴醚（慢）冠醚開鏈醚（快）配合物穩(wěn)定性（熱力學(xué)）：穴醚（穩(wěn)定）冠醚開鏈醚（易變）配合物形成速度（動力學(xué)）：22通過改變配位原子的種類，環(huán)的大小，拓?fù)涞瓤梢愿淖児诿杨惻潴w的選擇性通過改變配位原子的種類，環(huán)的大小，23Forrecognitionoftransitionmetal,lanthanideandactinideions,dependingonthecoordinationfeatureoftheionandthenature,numberanddispositionofbindingsites,aswellastotheirrigidty…Forrecognitionoftransition24剛性大環(huán)剛性大環(huán)25醫(yī)學(xué)上的應(yīng)用：抑制病毒、病菌生長，清除重金屬，抗腫瘤等。醫(yī)學(xué)上的應(yīng)用：抑制病毒、病菌生長，26光活性穴狀配體+銪或鋱光活性穴狀配體+銪或鋱27冠醚類似物結(jié)構(gòu)和分子識別的拓展1.對質(zhì)子的“配合”：內(nèi)部氫鍵冠醚類似物結(jié)構(gòu)和分子識別的拓展282.四面體識別—NH4+,TetrahedralRecognition2.四面體識別—NH4+,TetrahedralReco293.胺類離子的識別——AmmoniumRelatedSubstrates3.胺類離子的識別——AmmoniumRelatedS30主客體化學(xué)newppt課件314.中性分子的識別BindingandRecognitionofNeutralMoleculesHydrogenbonding,-stacking.4.中性分子的識別325.陰離子的識別,RecognitionofAnionicSubstrateRecognitionofhalidesandN3-5.陰離子的識別,RecognitionofAnio33主客體化學(xué)newppt課件34RecognitionofcarboxylatesRecognitionofcarboxylates35N-protonatedformscanbindanions.N-protonatedformscanbindan366.基于bipy的配位體6.基于bipy的配位體37主客體化學(xué)newppt課件38上：腸桿菌素+Fe3+Kf=1052下：腸桿菌素模擬物+Fe3+(6b):Kf=1059上：39Metallacrown,aclassofmetallamacrocycles金屬氮雜冠醚See,forexample, B.Kwak,etal.,Inorg.Chem.,1998,37,3599. S.Lin,etal.,J.C.S.,DaltonTrans.,2002,1595. S.X.Liuetal.,Angew.Chem.Int.Ed.,2001,40,1085. J.J.Bodwinetal.,Coord.Chem.Rev.,2001,216-217,489.Metallacrown,aclassofmetal4012-C-4O-CH2-CH2-O12-MC-4O-M-N-O12-C-4O-CH2-CH2-O12-MC-4O-41主客體化學(xué)newppt課件42LigandbindingmodeLigandbindingmode43M’m’Xx[A-MC-B]M’m’Xx[A-MC-B]44主客體化學(xué)newppt課件45主客體化學(xué)newppt課件46主客體化學(xué)newppt課件47主客體化學(xué)newppt課件48主客體化學(xué)newppt課件49主客體化學(xué)newppt課件50主客體化學(xué)newppt課件51主客體化學(xué)newppt課件52主客體化學(xué)newppt課件53AggregatesofmetallacrownAggregatesofmetallacrown54主客體化學(xué)newppt課件55主客體化學(xué)newppt課件56FormolecularrecognitionFormolecularrecognition57主客體化學(xué)newppt課件58主客體化學(xué)newppt課件59主客體化學(xué)newppt課件60Application: Magnetism Molecularrecognition,host-guestchemistry Sensor Liquidcrystal ……Application:613.1 Self-AssemblyofHelicalMetalComplexes:TheHelicatesLineararrayofmetalionsholdtogetherbybridgingpolytopicligandshelicallyarrangedaboutthecentralaxisthroughmetalions3.1 Self-AssemblyofHelicalM62DoubleHelicatesLigandthreads+MetalionsDoubleHelicates63Requirementforligands:

Easysynthesis Predictabilityofcoordinationbehavior desiredmetalbindingdomains properdispositionofthesedomainsinspace flexiblespacerMostusedligands:pyridine-typeligandsOthers:pyrrole-type,…Requirementforligands:64主客體化學(xué)newppt課件65Possibletypesofhelicateformedbyligandsofbidentatemetal-bindingdomainswithfour-coordinateandsixcoordinatemetalionsPossibletypesofhelicatefor66[4+4]helicate:[CuI2(12)2]2+Tetrahedralmetalcentres[4+4]helicate:[CuI2(12)2]2+67[6+6]helicate:[CdII2(24)2]4+Octahedralmetalcentres[6+6]helicate:[CdII2(24)2]4+68mixed[4+2]helicate:[CuI2(29)2]2+mixed[4+2]helicate:[CuI2(2969DifferentdoublehelicatesDifferentdoublehelicates70Heterotrinuclearcation[FeAg2(59)2]4+Heterotrinuclearcation[FeAg271主客體化學(xué)newppt課件72主客體化學(xué)newppt課件7322nmlength27nmlengthnanoarchitectures22nmlength27nmlengthnanoar74主客體化學(xué)newppt課件75主客體化學(xué)newppt課件76主客體化學(xué)newppt課件77Trisilver(I)complexof49Trisilver(I)complexof4978PositivecooparativityeffectsfordoublehelicalCu-52complexesPositivecooparativityeffects79LigandscontainingnucleisidesLigandscontainingnucleisides80DeoxyribonucleohelicatesDNHPositivelychargedPeripheryhydrogen-bondingbasesInteractionwithorbindingDNA?Deoxyribonucleohelicates81ChiralityofhelicatesChiralityofhelicates82主客體化學(xué)newppt課件83Triplehelicalcation[Co2(41)3]4+Tripl