Abstract
A series of d10 coordination polymers with the various spacer group of bidentate S-donor flexible ligands have been prepared and characterized. Polymers 1, 4, 5, 6, 7, 8, 13, 15, 16 and 17 have been characterized by the single crystal X-ray diffraction, FT-IR spectroscopy, X-ray powder diffraction (PXRD), elemental and TGA analysis. Inferred spectra and X-ray crystallographic analysis of compounds 2, 3, 9, 10, 11, 12, 14 have also been obtained. Compounds 2, 5, 11, 14 and 15 have two-dimensional structures while the other compounds have one-dimensional structures. Interestingly, the process and apparatus for growth of crystals 6 and 7 have a decisive influence in the 1D structure of these compounds. Polymer 6 with CuS2I coordination sphere was obtained by brunch tube method while polymer 7 with core structure of CuS4 has been found by solvothermal approach in which Cu(I) oxidized to Cu(II). In general spacer length of the ligands and coordination ability of the counter anions have a direct effect on the structure of the considered compounds.

The CPs are listed as follows:
{[Cu2(L4)3](PF6)2}n (1) [Hg L2 I]n (11)
[Cu2 L2 (SCN)2]n (2) [Hg2 L3 I4]n (12)
[Cu2 L3 (SCN)2]n (3) {[Hg3(L4)3I6](C6H9N3)0.33(H2O(3}n (13)
[Cu L4 SCN]n (4) [Hg2 L5 I4]n (14)
[Cu4(CN)4(L4)2]n (5) [Hg2 L4 Cl4]n (15)
[Cu L4 I]n (6) [Hg1.5(L4)1.5 (SeCN)3]n (16)
{[Cu (L4)2](SO4).(S8)0.5}n (7) [Cd L6 Cl2]n (17)
[Cu L6 SCN]n (8)
Theoretical study of compounds 1 and 4 have been performed by DFT calculations. Natural bond orbital analysis, structural, electronic and topological properties of these compounds were studied using the Gaussain 09 software at B3LYP/ 6-31+G** level of theory. TDOS and PDOS of these polymers have also been investigated at the same level of theory. In the case of 17 sorption kinetic and equilibrium were studied in detail by UV-Vis and solid fluorescence spectroscopy. In addition, the MIC, MBC and DNA cleavage activity of some compounds have also been studied.

In recent years, many researchers have undertaken considerable work on the design and synthesis of new silver(I) coordination polymers with soft and flexible dithioether ligands. However, the coordination chemistry of the flexible bis(imidazole-2-thione) ligands such as bis(3-methylimidazole-2-thione-1-yl) alkyl ligands has not been studied in detail in spite of the potentially useful applications that their coordination compounds might have in biomedical chemistry. In this thesis, we have successfully synthesized 26 silver(I)-based coordination polymers by varying the size and coordination ability of the counter anions as well as the length of the spacer of the bis(imidazole-2-thione) ligands Ln (n=2,3,4 and 6) together and with LN ligand. Compounds 1-3, 5-14 and 26 were fully characterized by using the infrared spectroscopy, elemental analysis, PXRD and single crystal X-ray diffraction. Compounds 4 and 15-23 were analysed only by infrared spectroscopy and X-ray crystallography. X-ray crystallographic analyses of the aforementioned compounds confirmed that although the Ln ligands have the same number of sulphur donor atoms, but by changing the spacer length of the ligands and varying the counterions, each of them displays a different type of coordination mode to the Ag centers. Antibacterial activity some of the synthesized compounds (1-14 and 26) were also studied. These compounds, in particular polymer 8 and 26 possess antibacterial activity against the selected strain of Gram-negative (Escherichia coli, Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus, Bacillus subtilis) bacteria. The molecular docking study of repeating unit rings of the polymers 5, 7, 8 and 26 with HAS.
a) Coordination polymers derived from the L6 ligand.
[Ag2 L6(NO3)2]n(1) [Ag2 L6 (CF3SO3)2 ]n(2)
[Ag2 L6(ClO4)(NO3)]n(3) [Ag L6]2 (PF6)2]n(4)
[Ag2 L6 Cl2]n(5) [Ag2 L6 Br2 ]n(6)
[Ag L6 I ]n(7) [Ag4 L6 (CN)4 ]n(8)
b) Coordination polymers derived from the L4 ligand.
[Ag2L4(NO3)2]n(9) {[AgL4]2[CF3SO3]2}n(10)
{[AgL4]2[BF4]2}n(11) {[AgL4]2[ClO4]2}n(12)
{[AgL4]2[PF6]2}n(13) {[AgL42][NO3)](S8)}n(14)
c) Coordination polymers derived from the L3 ligand.
[Ag2L3(NO3)2]n(15) {[Ag6L34(CF3SO3)4 ][CF3SO3]2}n(16)
{[Ag2L3(NO3)][PF6]}n (17) {[Ag2L3(NO3)][SbF6]}n(18)
{[Ag2L3(NO3)][ClO4]}n (19) {[Ag2L3(NO3)][BF4]}n(20)
d) Coordination polymers derived from the L2 ligand.
[Ag2L2(NO3)2]n(21) [Ag2L2(SO3CF3)2]n(22)
{[AgL2]2[BF4]2}n(23) {[AgL22][ClO4]}n(24)
{[Ag2L2]3[PF6]3}n(25)
e) Coordination polymer derived from the LN ligand.
[Ag3 LN (CN)3 ]n(26)
 

In order to investigate the influence of factors such as counter-ions, flexibility and steric hindrance of the linker ligands which play a key role in the structural determination of the iron(II) coordination polymers, complexes 1-10 have been designed and synthesized with different bidentate N-donor flexible ligands and fully characterized by single crystal X-ray diffraction, X-ray powder diffraction (XRPD), FT-IR spectroscopy, elemental and thermal analysis.

(1) {[Fe(bib)3](ClO4)2}n [bixH2](ClO4)2 ((6)
(2) {[Fe(bib)3](PF6)2}n [bibMeH](PF6) ((7)
(3) [Fe(bib)2(N3)2]n (8) [Fe(bib)2(NCS)2]n
(4) {[Fe(bix)2(NCS)2]•H2O}n (9) [Fe(bib)2(NCSe)2]n
(5) [Fe(bix)2(N3)2]n (10) [Fe(bpp)(NCS)2]

Moreover, attempt to synthesis the mix-valence and mix-metal complexes leads to synthesis and characteris compounds 11-15.

(11) [Zn(bpp)Cl2]
[Hg2(bpp)Cl4] (12(
(13) [Cu(bbd)(NCS)2]n
(14) [Cu2(SCN)2(tdmpp)]n
(15) [Cu2(bpp)2(N3)4]
In these compounds, the flexible ligands displaying different coordination behavior with different conformations such as anti-anti-anti and gauche-anti-anti arrangements. Thiocyanate and azide ligands also showed different coordination modes.