Departamento de Química Inorgánica, Universidad Autónoma de Madrid , 28049 Madrid, Spain.
Inorg Chem. 2013 Oct 7;52(19):11428-37. doi: 10.1021/ic401758w. Epub 2013 Sep 16.
Four new copper(II) coordination complexes, obtained by reaction of CuX2 (X = acetate or chloride) with thymine-1-acetic acid and uracil-1-propionic acid as ligands, of formulas [Cu(TAcO)2(H2O)4]·4H2O (1), [Cu(TAcO)2(H2O)2]n (2), [Cu3(TAcO)4(H2O)2(OH)2]n·4H2O (3), and [Cu3(UPrO)2Cl2(OH)2(H2O)2]n (4) (TAcOH = thymine-1-acetic acid, UPrOH = uracil-1-propionic acid) are described. While 1 is a discrete complex, 2-4 are one-dimensional coordination polymers. Complexes 2-4 present dc conductivity values between 10(-6) and 10(-9) S/cm(-1). The magnetic behavior of complex 2 is typical for almost isolated Cu(II) metal centers. Moderate-weak antiferromagnetic interactions have been found in complex 3, whereas a combination of strong and weak antiferromagnetic interactions have been found in complex 4. Quantum computational calculations have been done to estimate the individual "J" magnetic coupling constant for each superexchange pathway in complexes 3 and 4. Compounds 2-4 are the first known examples of semiconductor and magnetic coordination polymers containing nucleobases.
四种新型的铜（II）配合物，通过 CuX2（X=醋酸盐或氯化物）与胸腺嘧啶-1-乙酸和尿嘧啶-1-丙酸作为配体的反应得到，化学式为[Cu（TAcO）2（H2O）4]·4H2O（1）、[Cu（TAcO）2（H2O）2]n（2）、[Cu3（TAcO）4（H2O）2（OH）2]n·4H2O（3）和[Cu3（UPrO）2Cl2（OH）2（H2O）2]n（4）（TAcOH=胸腺嘧啶-1-乙酸，UPrOH=尿嘧啶-1-丙酸）。虽然 1 是一个离散的配合物，但 2-4 是一维配位聚合物。配合物 2-4 的直流电导率值在 10(-6)到 10(-9) S/cm(-1)之间。配合物 2 的磁行为典型地表现为几乎孤立的 Cu(II)金属中心。在配合物 3 中发现了中等弱的反铁磁相互作用，而在配合物 4 中发现了强和弱反铁磁相互作用的组合。已经进行了量子计算计算，以估计配合物 3 和 4 中每个超交换途径的个体“J”磁耦合常数。化合物 2-4 是首例已知的包含核碱基的半导体和磁性配位聚合物。
