Three Novel Inorganic−Organic Hybrid Arsenomolybdate Architectures Constructed from Monocapped Trivacant [AsIIIAsVMo9O34]6− Fragments with [Cu(L)2]2+ Linkers: From Dimer to Two-Dimensional Framework

Three novel inorganic−organic hybrid arsenomolybdates constructed from monocapped trivacant [As III As V Mo 9 O 34 ] 6− fragments with [Cu(en) 2 ] 2+ or [Cu(dap) 2 ] 2+ linkers, [Cu(en) 2 H 2 O] 2 {[Cu(en) 2 ][Cu(en) 2 As III As V Mo 9 O 34 ]} 2 ·4H 2 O ( 1 ), (H 2 en) 1.5 [Cu(en)(Hen)][As III As V Mo 9 O 34 ]·2H 2 O ( 2 ) (en = ethylenediamine), and [Cu(dap) 2 ] 4 [Cu(dap) 2 (H 2 O)][Cu(dap) 2 (As III As V Mo 9 O 34 ) 2 ]·2H 2 O ( 3 ) (dap = 1,2-diaminopropane), have been successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric (TG) analysis. Single-crystal structural analyses indicate that 1 − 3 all contain the peculiar monocapped trivacant [As III As V Mo 9 O 34 ] 6− subunit derived from the infrequent trivacant Keggin [A-α-As V Mo 9 O 34 ] 9− fragment with a capping {AsO 3 } group. Notably, 1 − 3 represent rare inorganic−organic hybrid heteropolymolybdate (HPM) containing [As III As V Mo 9 O 34 ] 6− subunits, which display the assembly from a zero-dimensional sandwich-type dimer, one-dimensional chain, to a two-dimensional layer by the [Cu(en) 2 ] 2+ or [Cu(dap) 2 ] 2+ linkers. Surface photovoltage spectroscopy (SPS) and electric field induced surface photovoltage spectroscopy (EFISPS) measurements for 1 − 3 indicate that only 3 has the n-type semiconductor characteristic.