The Study On Characterization Of Cage Structure Template-Synthesized By Thiophenboronic Acid And Phenylboronic Acid Derivatives

In this paper, three functionalized coordination primitives containing Mn, Co and Fe metal ions with 2,6-diformyl-4-methylphenol (H3dfmp) and 1,2-cyclohexanedione dioxide (H2dpg) working as ligands were formed. These primitives as connecting blocks can coordinate with B-O covalent bonds which were from organic borate ligands to obtain ten metal-borate-organic complexes and all crystals of them. Also, their structures and electrochemical properties were characterized and analyzed. One representative complex was chosen to get electrochemical polymerization by repeative CV scan.Two bimetal center coordination primitives 1 and 2 were obtained with H3dfmp as ligand which was dealing with manganese chloride and cobalt chloride, respectively. The primitive 1 reacted with 2-thienylboronic acid,3-thienylboronic acid and 5-formylthiophene-2-boronic acid to form complexes la (Et3NH[(2-C4H3S)BⅢ{(H3L1)3MnⅡ2}(2-C4H3S)BⅢ],1b (Et3NH[(3-C4H3S)BⅢ{(H3L1)3MnⅡ2}(3-C4H3S)BⅢ], lc(Et3NH[(C5H3OS)BⅢ{(H3L1)3MnⅡ2}(C5H3OS)BⅢ], respectively. The primitive 2 reacted with 2-thienylboronic acid and 3-thienylboronic acid to obtain 2a (Et3NH[(2-C4H3S)BⅢ{(H3L1)3CoⅡ2}(2-C4H3S)BⅢ] and 2b (Et3NH[(3-C4H3S)BⅢ{(H3L1)3CoⅡ2}(3-C4H3S)BⅢ]. One-metal center coordination primitive 3 was obtained,when H2dpg was used as raw material and dealing with ferric tetrafluoroborate. Then primitive 3 reacted with 2-thienylboronic acid, 3-thienylboronic acid,5-formylthiophene-2-boronic acid,4-aminophenylboronic acid hydrochloride and 4-cyanophenylboronic acid to get complexes 3a ((2-C4H3S)BⅢ (H2L2)3FeⅡ(2-C4H3S)BⅢ)),3b ((3-C4H3S)BⅢ(H2L2)3FeⅡ(3-C4H3S)BⅢ)),3c ((C5H3OS)BⅢ(H2L2)3FeⅡ(C5H3OS)BⅢ)),3d ((C6H6N)BⅢ(H2L2)3FeⅡ(C6H6N)BⅢ)), 3e ((C7H4N)BⅢ(H2L2)3FeⅡ(C7H4N)BⅢ)), respectively.The single crystal structure analysis showed that the la belonged to monoclinic system, C 2/c space group. The parameters of the single crystal:a=26.024 (2) A, b =14.9755(10)A, c=23.7016(19)A;a=90.00°, β=97.225(3)°,γ=90.00° Volume=9163.7(12)A3,Z=8,F(000)=4080,R1=0.1124,wR2=0.2811.The single crystal structure analysis showed that the 1b belonged to monoclinic system,C 2/c space group.The parameters of the single crystal:a=25.9715(19)A, b=15.3621(11)A,c=23.1650(19)A;α=90.00°,β=97.041(2)°,γ=90.00 °;Volume=9172.6(12)A3,Z=8,F(000)=4144,R1=0.0657,wR2=0.1524.The single crystal structure analysis showed that the l c belonged to monoclinic system,C 2/c space group.The parameters of the single crystal:a=25.5334(19)A, b=15.0183(11)A,c=24.5057(15)A;α=90.00(2)°,β=100.475(2)°,γ 90.00(2)°;Volume=9240.5(11)A3,Z=8,F(000)=4384,R1=0.0861,wR2= 0.1897.The single crystal structure analysis showed that the 2a belonged to monoclinic system,C 2/c space group.The parameters of the single crystal:a=25.7622(18)A,b =14.9182(11)A,c=23.7997(15)A;α=90.00(2)°,β=981384(2)°,γ=90.00(2) °;Volume=9049.1(11)A3,Z=8,F(000)=4128,R1=0.0809,wR2=0.2311.The single crystal structure analysis showed that the 2b belonged to monoclinic system,C 2/c space group.The parameters of the single crystal:a=26.0227(13)A, b=15.2505(7)A,c=23.1388(12)A;α=90.00°,β=97.262(2)°,γ=90.00 °;Volume=9109.2(8)A3,Z=8,F(000)=4272, R1=0.0621,wR2=0.1633.The single crystal structure analysis showed that the 3a belonged to Triclinic system,C 2/c space group.The parameters of the single crystal:a=11.6714(6)A,b =11.9925(6)A,c=13.3816(7)A;α=92.247(2)°, β=103.882(2)°, γ= 115.807(2)°;Volume=1614.69(14),Z=2,F(000)=772,R1=0.0737,wR2= 0.1089.The single crystal structure analysis showed that the 3b belonged to monoclinic system,C 2/c space group.The parameters of the single crystal:a=11.6598(6)A,b =12.1047(7)A,c=13.3380(8)A;α=91.612(2)°,β=103.915(2)°, γ=116.591 (2)°;Volume=1613.86(16),Z=2,F(000)=772,R1=0.0616,wR2=0.0891.The single crystal structure analysis showed that the 3c belonged to monoclinic system,C 2/c space group.The parameters of the single crystal:a=11.0977(6)A,b =11.5612(6)A,c=15.1249(8)A;α=67.669(2)°,β=86.181(2)β,γ=74.285 (2)°;Volume=1726A3,Z=2,F(000)=848,R1=0.0851,wR2=0.2291.The single crystal structure analysis showed that the 3d belonged to monoclinic system, P21/c space group. The parameters of the single crystal:a=14.351(17)A, b=15.588(2)A, c=17.263 (2) A; α=90.00°,β=102.686(2)°, γ=90.00°; Volume=3814.2(9)A3, Z=4, F(000)=1792,R1=0.0824, wR2=0.1923.The single crystal structure analysis showed that the 3e belonged to monoclinic system, P21/n space group. The parameters of the single crystal:a=14.3351(17)A, b=15.588 (2) A, c=17.263 (2) A; α=90.00°, β=98.590 (3)°, γ=90.00°; Volume=3814.2(9)A3,Z=4, F(000)=4792, R1=0.0824, wR2=0.1923.The structure of complexes obtained were confirmed through infrared(IR) and mass spectrometry(MS).Also, electrochemical properties and redox properties of these complexes were analyzed and discussed using cyclic voltammetry(CV). Due to the presence of metals in these complexes,electron conduction of complex intramolecular exhibited transformation of different metal valence, that is, pairs of redox peaks, which were realized by electron coupling.Complex 1a was chosen to get electrochemical polymerization poly-1a by repeative CV scan. By the study on characterization UV of poly-1a, it proves the successful preparation of poly-1a.