Four new deficient compounds in the R6B2C2QI4 family, LasCaSn2.75S4 1, Y6A10.67Ge2S14 2, Er5.33Si4S14 3 and Er4Ge4SI4 4, have been obtained via a precursor/flux method. Single-crystal analysis indicated that their crystal structures consist of three types of building blocks： RS7 （R = La/Ca for 1, R = Y for 2, R = Er for 3 and 4） mono-triangonal prism, CS6 （C = A1 for 1, C = Sn（2） for 2, C = Si（2） for 3, C = Ge（2） for 4） octahedron, and BS4 （B = Si for 1, B = Sn（1） for 2, B = Si（1） for 3, B = Ge（1） for 4） tetrahedron, as any other compounds belong to the R6B2C2Q14 family.
The reaction of CdCl2 with 6,7-dicyanodipyridoquinoxaline （DICNQ） by solvothermal reaction gives rise to a coordination polymer [CdCl2（DICNQ）]n 1. Single-crystal X-ray diffraction analysis reveals that the compound in space group Pbcn creates 1-D chloro-bridging chains. Crystal data for 1： a = 6.756（1）, b = 35.371（6）, c = 7.027（1）A , V = 1679.1（5） A^3, Z = 4.00, C16H6CdCl2N6, Mr = 465.57, Dc = 1.842 g/cm^3, μ = 1.630 mm-1, F（000） = 904, S = 1.005 and T = 293（2） K. The final R = 0.0376 and wR = 0.1029 for 1291 observed reflections with I 〉 2σ（I）, and R = 0.0499 and wR = 0.1125 for all data. The 1-D chloro-bridging chains are parallel-stacked in the a and b directions, and further stabilized through π-stacking interactions, hydrogen-bonding interactions and C≡N···π interactions to generate a 3-D structure. Compound 1 displays intense bluish-green photoluminescence from the intraligand charge-transfer of the DICNQ ligand and the Cl--to-DICNQ charge-transfer mechanism which is probed by the density of states （DOS） calculations.
