A chiral two-dimensional coordination polymer based on Cu-II and (S)-4,4 %26apos;-bis(4-carboxyphenyl)-2,2 %26apos;-bis(diphenylphosphinoyl)-1,1 %26apos;-binaphthyl: Synthesis, structure, and magnetic and optical properties

作者：Lestari Witri Wahyu; Loennecke Peter; Streit Huayna Cerqueira; Schleife Frederik; Wickleder Claudia^*; Hey Hawkins Evamarie

来源：Inorganica Chimica Acta, 2014, 421: 392-398.

DOI：10.1016/j.ica.2014.06.006

• Coordination polymers
• Copper
• BINAPO derivatives
• Magnetic properties
• Catalysis
• Optical properties

The functionalized binaphthyl derivative (S)-4,4%26apos;-bis(4-carboxyphenyl)-2,2%26apos;-bis(diphenylphosphinoyl)-1,1%26apos;-binaphthyl (H2L) was employed as linker in the synthesis of the chiral Cu-II-based two-dimensional network {[Cu-2(L)(2)(dmf) (2)]center dot H2O center dot 9 dmf}(n) (1). Single-crystal X-ray analysis showed a two-dimensional structure with a copper paddle wheel as secondary building unit. One dmf molecule is additionally axially coordinated to each Cu cation. A lamellar structure results consisting of alternating [Cu-2(L)(2)(dmf)(2)](n) and solvent (dmf, H2O) layers. According to DTA/TG measurements the coordinated dmf molecules are released at about 320 degrees C, followed by decomposition around 460 degrees C. Magnetic susceptibility measurements on 1 indicate strong antiferromagnetic coupling between the two metal centers in Cu-2(L)(2)(dmf)(2). Compound 1 exhibits ligand-based luminescence, assigned to the S-1 --%26gt; S-0 transition of the aromatic units. Moreover, the emission spectrum of 1 is blueshifted in comparison to H2L, due to different dihedral angles within the respective structures. Activated 1 (heating to 300 degrees C under vacuum for 3 h) showed low activity in the catalytic cyanosilylation of benzaldehyde (up to 27.1% conversion) and the isomerization of alpha-pinene oxide to campholenic aldehyde (up to 15.5% conversion).

• 出版日期2014-9-1