National Single Crystal X-ray Diffraction Facility and Department of Chemistry, IIT Bombay, Powai, Mumbai, India.
Dalton Trans. 2010 Feb 14;39(6):1447-9. doi: 10.1039/b918761h. Epub 2009 Dec 3.
The single crystals of discrete hydrated [(OAc)Cu(mu-hep)(2)Cu(OAc)].2H(2)O (.2H(2)O) and [(OAc)Cu(mu-hep)(2) Cu(O(n)Pr)].2H(2)O (.2H(2)O) (the lattice H(2)O molecules exist as a tetrameric water cluster, hep-H = 2-(2-hydroxyethyl)pyridine), OAc(-) = acetate and O(n)Pr(-) = n-propionate) undergo single-crystal to single-crystal (SCSC) transformations to the dehydrated and , respectively, under the influence of heat. The reverse SCSC processes of /-->.2H(2)O/.2H(2)O involving the regeneration of the lattice water tetramers take place on exposure of / to water vapour. However, the blue single crystal of discrete hydrated [(O(n)Pr)Cu(mu-hep)(2)Cu(O(n)Pr)].2H(2)O (.2H(2)O), incorporating the two bulkier O(n)Pr(-) terminal bidentate ligands, irreversibly converts to the green single crystal of a unique discrete tetrameric [Cu(4)(mu(3)hep)(2)(mu-hep)(2)(mu-O(n)Pr)(2)(O(n)Pr)(2)] () with double open cubane core either by heating or by a simple vapour diffusion technique via the breaking and forming of multiple covalent bonds.
离散水合[(OAc)Cu(mu-hep)(2)Cu(OAc)].2H(2)O(.2H(2)O)和[(OAc)Cu(mu-hep)(2)Cu(O(n)Pr)].2H(2)O(.2H(2)O)(晶格中的 H(2)O 分子以四聚体水簇的形式存在,hep-H = 2-(2-羟基乙基)吡啶),OAc(-) = 醋酸根和 O(n)Pr(-) = 正丙酸盐)在受热影响下分别经历从单晶到单晶(SCSC)的转变,脱去晶格水。/-->.2H(2)O/.2H(2)O 的反向 SCSC 过程涉及晶格水四聚体的再生,在暴露于水蒸气时发生。然而,包含两个较大的 O(n)Pr(-)端双齿配体的离散水合[(O(n)Pr)Cu(mu-hep)(2)Cu(O(n)Pr)].2H(2)O(.2H(2)O)的蓝色单晶会不可逆地转化为绿色单晶,形成独特的离散四聚体[Cu(4)(mu(3)hep)(2)(mu-hep)(2)(mu-O(n)Pr)(2)(O(n)Pr)(2)](()),其具有双开口立方烷核,通过加热或简单的蒸气扩散技术均可实现,该技术通过多个共价键的断裂和形成来实现。