Two-Dimensional Rhombohedral Grid Coordination Polymers [M(bbbt)₂(NCS)₂]_n (M = Co, Mn, or Cd; bbbt = 1,1‘-(1,4-butanediyl) bis-1H-benzotriazole):  Synthesis, Crystal Structures, and Third-Order Nonlinear Optical Properties

Abstract

In this paper, treatment of 1,1'-(1,4-butanediyl) bis-1H-benzotriazole (bbbt) and KSCN with Co(II), Mn(II), or Cd(II) afforded three two-dimensional rhombohedral grid coordination polymers [M(bbbt)(2)(NCS)(2)](n)(M = Co, 1; Mn, 2; Cd, 3). The two-dimensional rhombohedral grids are parallel to the crystallographic ac plane. The rhombohedral grid consists of 44-membered rings of M(4)(bbbt)(4), and gives the dimensions of 12.913 x 10.764 A for polymer 1, 13.106 x 10.797 A for polymer 2, and 13.256 x 10.870 A for polymer 3. The three polymers' third-order nonlinear optical (NLO) properties were determined by Z-scan technique in DMF solution. The results show that all three polymers show very large NLO absorption and strong NLO refraction properties. The third-order NLO absorptive coefficients alpha(2) are 5.4 x 10(-9) m W(-1) for polymer 1, 5.2 x 10(-9) m W(-1) for polymer 2, and 5.0 x 10(-9) m W(-1) for polymer 3. The alpha(2) values are larger than those of all the reported cluster compounds. The NLO refractive index values n(2) of the three polymers are 5.73 x 10(-19), 3.55 x 10(-19), and 3.07 x 10(-19) m(2) W(-1), respectively. Their hyperpolarizability gamma values are calculated to be 2.40 x 10(-30) esu for polymer 1, 1.52 x 10(-30) esu for polymer 2, and 1.50 x 10(-30) esu for polymer 3. The gamma values are comparable to those of clusters and better than those of organometallic compounds, semiconductors, and fullerene.

Structures and enhanced third-order nonlinear optical performance of four complexes investigated by thin film Z-scan technique

“…The corresponding third-order susceptibilities v (3) of complexes 1, 2, 3 and 4 are 2.74 9 10 -9 , 12.24 9 10 -9 , 42.78 9 10 -9 and 189.32 9 10 -9 esu, respectively. These values are much larger than those of CPs reported in solution and of pure semiconductors [13][14][15][16][17][27][28][29]. Hence, these complexes appear to be good candidates for third-order NLO materials.…”

“…Before the preparation of compound films, we measured the XRD patterns of the complexes and compared them Although the third-order nonlinear properties of some CPs have been reported [13][14][15][16][17]27], these data were from the solution state. Therefore, we studied the third-order NLO properties of these neat compounds in thin films by Zscan techniques.…”

“…These compounds show a range of NLO optical properties [14,15]. For instance, the complex [M(bbbt) 2 (NCS) 2 ] n (M=Co, Mn or Cd, bbbt = 1, 1 0 -(1,4-butanediyl)bis-1H-benzotriazole) shows very large NLO absorption and strong NLO refraction properties [16]. The complex [Ag 10 (dcapp) 4 ]Á2(OH)Á12H 2 O has a very strong NLO absorption effect [17].…”

Synthesis, characterization and third-order nonlinear optical properties of bromo[tri-α-(2,4-dimethyl-3-pentyloxy)subphthalocyanine]boron complex

“…All of the values are comparable to those of the reported good NLO materials. In addition, the effects of cone-shaped molecular structure and axially heavy-atom (Br) substitution on third-order NLO properties are discussed.Organic compounds and organometallic complexes with p-electron delocalization, such as phthalocyanines and related compounds [1][2][3][4][5][6][7], fullerene (C 60 ) and its relatives [8][9][10][11][12], metal clusters and their polymers [13,14], have received significant attention in the last two decades because of their large and fast nonlinear optical response and potential applications in optical communication, data processing, optical switching, optical limiting devices, etc. Current research aims to develop materials with improved/optimized nonlinear optical properties via rational design and synthesis.…”

Synthesis, crystal structure and luminescent properties of a novel cadmium coordination polymer with unprecedented one-dimensional hetero-triple-stranded chain

“…Contrary to rigid spacers, the flexible ligand, which can adopt various conformations, may induce coordination polymers with novel topologies. Compared to flexible ligands based on other heterocycles such as imidazole [8][9][10][11][12][13], benzoimidazole [14,15] and triazole [16][17][18][19][20][21], the flexible benzotriazole ligands are relatively less studied [22][23][24]. On the other hand, polynuclear d 10 metal complexes have attracted extensive interest in recent years in that they not only exhibit appealing structures but also photoluminescent properties [25][26][27][28][29].…”