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机构地区:[1]福建师范大学高分子研究所,福建师范大学化学系
出 处:《应用化学》1994年第5期31-35,共5页Chinese Journal of Applied Chemistry
摘 要:配位聚合物PAAm-CuCl_2和cuCl_2·2H_2O的Cu ̄(2+)2pXPS谱上都有Shake-up峰,其与各自的Cu ̄(2+)2p3/2肩峰或主峰距离ΔEs2或ΔEs分别为8.7和8.6eV;但配位聚合物Cu(Ⅱ)-PVA却无此峰.由此推定,前者的Cu ̄(2+)是以sp ̄3杂化轨道接受PAAm4个链节单元C-N上N的孤对电子部分转移形成配位键;而Cu(Ⅱ)-PVA配位聚合物中的Cu ̄(2+)却以dsp ̄2杂化轨道接受PVA4个链节单元侧基O的孤对电子部分转移,产生配位键,即Cu ̄(2+)与PAAm或PVA的链节单元配位比均是1:4,此结果与电导率法测定PAAm-CuCl_2的配位比相同.The shake-up peaks are observed on XPS spectra of the coordination complexPAAm-CuCl2 and CuCl2·2H2O and they have a distance to Cu2+2p3/2 shoulder or main peak(ΔEs2=8.7eV or ΔEs=8.6eV)respectively.No shake-up peak in XPS spectrum was foundfor Cu(Ⅱ)-PVA complex.It is concluded that the coordination bond in PAAm-CuCl2 isformed in result of the acceptance of sp3 hybrid orbitals with the nonpair electrons partiallytransfered from N of four C-N units of PAAm,whereas in Cu(Ⅱ)-PVA it is formed in re-sult of the acceptance of dsp2 hybrid orbitals with partial transfered nonpair electrons on theside O in four chain units of PVA.The ratio of coordination betvveen Cu2+ and PAAm orPVA is thus one to four,as was determined for Cu2+ and PAAm by electric conductivitymeasurement.
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