Shankar Bhaskaran, Marimuthu Rajendiran, Deval Sathiyashivan Shankar, Sathiyendiran Malaichamy
School of Chemistry, University of Hyderabad , Hyderabad 500 046, India.
Inorg Chem. 2016 May 2;55(9):4537-44. doi: 10.1021/acs.inorgchem.6b00371. Epub 2016 Apr 21.
Flexible hexatopic ligands, 1,2,3,4,5,6-hexakis(1H-naphtho[2,3-d]imidazol-1-ylmethyl)benzene (L(2)) and 1,2,3,4,5,6-hexakis(4,5-diphenylimidazol-1-ylmethyl)benzene (L(3)), containing six neutral naphthanoimidazolyl and 4,5-diphenylimidazolyl N donors were synthesized and used to assemble M6L6L'-type [M = Re(CO)3, L = anionic angular rigid NN donors, and L' = flexible hexatopic N donors] spheroid metallacycles. These molecules with a diameter of ∼17 Å were obtained from Re2(CO)10, H-L (imidazole, benzimidazole, and naphthanoimidazole), and L' [1,2,3,4,5,6-hexakis(benzimidazol-1-ylmethyl)benzene (L(1)), L(2), and L(3)] in a one-step process. Ligands L(2) and L(3) were characterized by elemental analysis, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and (1)H NMR spectroscopy. Metallacycles 1-5 were characterized by elemental analysis, ESI-TOF-MS, Fourier transform infrared spectroscopy, and single-crystal X-ray diffraction analysis. Molecules 1, 2, and 4 can be considered as metallocavitands and contain multiple solvent-accessible receptors, i.e., two metallocalix[3]arene units and six/four calix[4]arene-/cleft-shaped receptors, on the surface. Guests such as acetone molecules could be accommodated in the calix[4]arene/cleft-shaped receptor of the metallocavitands.
合成了含有六个中性萘并咪唑基和4,5-二苯基咪唑基氮供体的柔性六齿配体1,2,3,4,5,6-六(1H-萘并[2,3-d]咪唑-1-基甲基)苯(L(2))和1,2,3,4,5,6-六(4,5-二苯基咪唑-1-基甲基)苯(L(3))，并用于组装M6L6L'-型[M = Re(CO)3，L = 阴离子角形刚性NN供体，L' = 柔性六齿氮供体]球形金属环。这些直径约为17 Å的分子是通过一步法由Re2(CO)10、H-L(咪唑、苯并咪唑和萘并咪唑)和L'[1,2,3,4,5,6-六(苯并咪唑-1-基甲基)苯(L(1))、L(2)和L(3)]得到的。配体L(2)和L(3)通过元素分析、电喷雾电离飞行时间质谱(ESI-TOF-MS)和1H NMR光谱进行表征。金属环1-5通过元素分析、ESI-TOF-MS、傅里叶变换红外光谱和单晶X射线衍射分析进行表征。分子1、2和4可被视为金属穴体，其表面含有多个溶剂可及的受体，即两个金属杯[3]芳烃单元和六个/四个杯[4]芳烃/裂缝形受体。丙酮分子等客体可容纳在金属穴体的杯[4]芳烃/裂缝形受体中。
