Hydrothermal synthesis, crystal structure and optical properties of a 2-D heterometallic iodoplumbate

Heterometal silver/copper(I) modulated thermochromism of two isostructural iodoplumbates

“…The fundamental building unit of 1 consists of three and one half Pb atoms, one Cu atom, eleven I atoms and one solvated [Y(DMF) 8 antiprismatic slightly distorted towards dodecahedral geometry ( Fig. S1) with Y-O bond lengths ranging from 2.293(12) to 2.378 (13)Å, which is comparable to the compound [Y(DMF) 8 ] [Ag 6 (μ 4 À I) 2 (μ 3 À I) 2 (μ À I) 5 ] 11 [28].…”

“…Organic-inorganic hybrid iodometallates of group 14 (Sn(II), Pb (II)) and group 15 (Bi(III)) are attractive due to their potential electronic [1][2][3][4] or optical properties [5][6][7], and incorporation of heterometallic atoms into iodometallates based on BiI 3 /PbI 2 can contribute to their structural and functional flexibility, such as semiconducting [8,9], fluorescent [10,11] and thermochromic [8,12] properties. To date, besides of a few neutral [Pb 3 I 10 Cu 4 (phen) 2 ] n , PbI 4 Cu 2 (PPh 3 ) 4 , [Bi(phen)I 4 Ag(phen)] n , [PbCu 6 I 8 ](PPh 3 ) 6 , [PbAg 2 (PPh 3 ) 2 I 4 ] n Á [PbI 2 (DMF) 2 ] n and [Pb(bipy)Ag 3 I 5 ] n [8][9][10][11], the reported heterometallic iodobismuthates/iodoplumbates mainly include the clustered [Cu 2 (CH 3 CN) 2 Bi 2 I 10 2 À ], [Bi 4 [10,[12][13][14][15][16][17][18].…”

“…To date, besides of a few neutral [Pb 3 I 10 Cu 4 (phen) 2 ] n , PbI 4 Cu 2 (PPh 3 ) 4 , [Bi(phen)I 4 Ag(phen)] n , [PbCu 6 I 8 ](PPh 3 ) 6 , [PbAg 2 (PPh 3 ) 2 I 4 ] n Á [PbI 2 (DMF) 2 ] n and [Pb(bipy)Ag 3 I 5 ] n [8][9][10][11], the reported heterometallic iodobismuthates/iodoplumbates mainly include the clustered [Cu 2 (CH 3 CN) 2 Bi 2 I 10 2 À ], [Bi 4 [10,[12][13][14][15][16][17][18]. Although Pb is a neighboring element of Bi with similar cation size and octahedral coordination character [13,19], their different oxidation states endow them with specific structural buildings and functional features.…”

“…Although Pb is a neighboring element of Bi with similar cation size and octahedral coordination character [13,19], their different oxidation states endow them with specific structural buildings and functional features. Typically, thermochromism as an interesting phenomenon has attracted much attention in the field of iodobismuthate or iodoplumbate hybrids [8,12,[20][21][22][23][24][25][26][27]. Differing from the thermochromic iodobismuthates, only a handful of thermochromic layered perovskite-type iodoplumbates [22][23][24][25][26][27] and two thermochromic heterometallic iodoplumbates ([Co(phen) 3 ] 2 [Pb 3 Cu 6 I 16 ] Á C 2 H 5 OH [12] and [Pb 3 I 10 Cu 4 (phen) 2 ] n ) [8] have been reported, which is likely due to their larger energy gap and limited response of their structures to the temperature.…”

“…Typically, thermochromism as an interesting phenomenon has attracted much attention in the field of iodobismuthate or iodoplumbate hybrids [8,12,[20][21][22][23][24][25][26][27]. Differing from the thermochromic iodobismuthates, only a handful of thermochromic layered perovskite-type iodoplumbates [22][23][24][25][26][27] and two thermochromic heterometallic iodoplumbates ([Co(phen) 3 ] 2 [Pb 3 Cu 6 I 16 ] Á C 2 H 5 OH [12] and [Pb 3 I 10 Cu 4 (phen) 2 ] n ) [8] have been reported, which is likely due to their larger energy gap and limited response of their structures to the temperature. Although some explanations have been suggested for the above phenomenon, such as the temperature induced phase transition and lattice contraction, this kind of thermochromic property can generally be attributed to the distortion of iodoplumbate framework and consequent changes of absorption position and intensity, which implies the decisive roles of chain-like organic amines and heterometallic components.…”