Crystal structures of amarine and isoamarine and copper(I) coordination chemistry with their allylation products

The crystal structures of amarine (1) and isoamarine (2), important intermediates in the preparation of 1,2-diphenyl-diaminoethane, were successfully determined. Their allylation products, 1,3-diallyl amarine (1)(CH2CHCH2)2Br (3) and isoamarine bromide (2)(CH2CHCH2)2Br (4) [the crystal structures of (1)(CH2CHCH2)2PF6(3-Br + PF6) and (2)(CH2CHCH2)2PF6 (4-Br + PF6) are also successfully determined to confirm allylation products], react with CuBr to afford (1)2(CH2CHCH2)4(Cu2Br4) (5) and (2)(CH2CHCH2)2(Cu2Br3) (6), respectively. Crystal structures of 5 and 6 reveal that 5 is an anion discrete complex without olefin moiety coordination, and 6 has a 1D infinite chain with olefin moiety coordination as a bridging spacer. The fluorescent emission spectra of 5 (λemax = 570 nm) and 6 (λemax = 642 nm) were measured, and display a significant difference that can be used for solid state fluorescent sensing them.

Graphical abstractThe crystal structures of amarine (1) and isoamarine (2), important intermediates in the preparation of 1,2-diphenyl-diaminoethane, were successfully determined. Their allylation products, 1,3-diallyl amarine (1)(CH2CH=CH2)Br (3) and isoamarine bromide (2)(CH2CH=CH2)Br (4) [the crystal structures of (1)(CH2CH=CH2)2PF6 (3-Br + PF6) and (2)(CH2CH=CH2)2PF6 (4-Br + PF6) are also successfully determined to confirm allylation products], react with CuBr to afford (1)2(CH2CH=CH2)4(Cu2Br4) (5) and (2)(CH2CH=CH2)2(Cu2Br3) (6), respectively. Crystal structures of 5 and 6 reveal that 5 is an anion discrete complex without olefin moiety coordination, and 6 has a 1D infinite chain with olefin moiety coordination as a bridging spacer. The fluorescent emission spectra of 5 (λemax = 570 nm) and 6 (λemax = 642 nm) were measured, and display a significant difference that can be used for sensing them.Figure optionsDownload full-size imageDownload as PowerPoint slide