Silver() complexes with a P-N hybrid ligand and oxyanions: synthesis, structures, photocatalysis and photocurrent responses

Reactions of a P-N hybrid ligand, N , N -bis(diphenylphosphanylmethyl)-3-aminopyridine (3-bdppmapy), with silver oxysalts including AgNO 3 , AgOAc, AgBz (Bz = benzoate) and AgSal (Sal = salicylate) under different reaction conditions give rise to seven coordination compounds {[Ag 4 (μ-η,η-NO 3 ) 2 (μ-η,η 2 -NO 3 ) 2 ](3-bdppmapy) 2 } n ( 1 ), {[Ag 4 (μ-η,η 2 -NO 3 ) 4 ](3-bdppmapy) 2 } n ( 2 ), {[Ag 2 (μ-η 2 -OAc)(μ-η,η 2 -OAc)] 2 (3-bdppmapy) 2 } n ( 3 ), [Ag 2 (Bz)(μ-η,η 2 -Bz)(H 2 O)] 2 (3-bdppmapy) 2 ( 4 ), {[Ag 4 (μ-η 2 -Bz) 2 (μ-η,η 2 -Bz) 2 ](3-bdppmapy) 2 } n ( 5 ), {Ag(Sal)(3-bdppmapy)} n ( 6 ) and {[Ag 4 (Sal) 2 (μ-η,η 2 -Sal) 2 ](3-bdppmapy) 2 } n ( 7 ). Single crystal X-ray analyses reveal that 1 , 5 and 7 have similar 1D chain structures constructed by [Ag 4 (μ-η 2 -Ox) 2 (μη,η 2 -Ox) 2 ] units ( 1 : Ox − = NO 3 − ; 5 : Ox − = Bz − ) or [Ag 4 (Sal) 2 (μ-η,η 2 -Sal) 2 ] units ( 7 ) and double 3-bdppmapy bridges. Compound 2 has a 2D layer structure derived from [Ag 4 (μ-η,η 2 -NO 3 ) 4 ] units and single 3-bdppmapy bridges. 3 displays another 2D layer structure formed by [Ag 2 (μ-η 2 -OAc)(μ-η,η 2 -OAc)] units and double 3-bdppmapy bridges. 4 shows a discrete tetranuclear structure formed by two [Ag 2 (Bz)(η,η 2 ,μ-Bz)(H 2 O)] units and a pair of 3-bdppmapy bridges, while 6 adopts a 1D chain composed by [AgSal] units and single 3-bdppmapy bridges. 6 and 7 as representative samples display high catalytic activity toward the photodegradation of rhodamine B (RhB) in water. Compound 7 shows a better photocatalytic performance than that of 6 , which correlates well with the differences in their anodic photocurrent responses and their HOMO-LUMO energy gaps derived from the density function theory (DFT) calculations. The formation of 6 and 7 from AgSal and 3-bdppmapy provides a new approach to the design and assembly of Ag( i )-supported CPs with interesting structural architectures and higher photocatalytic activity. Silver( i ) complexes with a P-N ligand and oxyanion show excellent catalytic photodegradation performances, which correlate with their photocurrent responses.