Cooperative metal–ligand influence on the formation of coordination polymers, and conducting and photophysical properties of Tl(i) β-oxodithioester complexes (original) (raw)

2018, Dalton Transactions

Abstract

Eight novel luminescent and semiconducting Tl(i) β-oxodithioester complexes forming 1D/2D coordination polymeric structures were investigated using single crystal X-ray diffraction.

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References (24)

  1. Yield: (0.204 g, 66%). Anal. Calcd for: C 18 H 14 OS 2 (310.43): C 69.64, H 4.55%. Found: C 69.57, H 4.68%. IR (KBr, cm -1 ): = 1140 ( C-OH ), 1580 ( C=C ), 1227 ( C=S ).
  2. H NMR (500.15
  3. MHz, CDCl 3 ): δ 2.70 (s, 3H, -SCH 3 ), 6.87 (s, 1H, -CH=C-), 7.25-8.52 (m, 9H, -C 14 H 9 ), 15.37 (s, 1H, -C(OH)-) ppm. 13 C{ 1 H} NMR (125.03 MHz, CDCl 3 ): δ 17.11 (-SCH 3 ), 115.17 (- CH=C-). 124.72, 125.31, 126.74, 127.26, 128.47, 129.23, 131.00, 134.06 (-C 14 H 9 ), 170.18 (- C(OH)-), 218.69 (-C=S) ppm.
  4. Yield: (0.200 g, 88%). Anal. Calcd for: C 10 H 9 FOS 2 (228.31): C 52.61, H 3.97%. Found: C 52.42, H 4.10%. IR (KBr, cm -1 ): = 1165 ( C-OH ), 1601 ( C=C ), 1229 ( C=S ).
  5. H NMR (500.15
  6. MHz, CDCl 3 ): δ 2.59 (s, 3H, -SCH 3 ), 6.83 (s, 1H, -CH=C-), 7.04-7.83 (m, 4H, -C 6 H 4 F), 15.03 (s, 1H, -C(OH)-) ppm. 13 C{ 1 H} NMR (125.03 MHz, CDCl 3 ): δ 17.20 (-SCH 3 ), 107.61 (- CH=C-), 122.95, 129.63, 134.58, 136.39, (-C 6 H 4 F), 167.09 (-C(OH)-), 216.62 (-C=S) ppm.
  7. Yield: (0.208 g, 85%). Anal. Calcd for: C 10 H 9 ClOS 2 (244.76): C 49.07, H 3.71%. Found: C 48.95, H 3.85%. IR (KBr, cm -1 ): = 1121 ( C-OH ), 1582 ( C=C ), 1234 ( C=S ).
  8. H NMR (500.15
  9. MHz, CDCl 3 ): δ 2.64 (s, 3H, -SCH 3 ), 6.88 (s, 1H, -CH=C-), 7.39-7.80 (m, 4H, -C 6 H 4 Cl), 15.03 (s, 1H, -C(OH)-) ppm. 13 C{ 1 H} NMR (125.03 MHz, CDCl 3 ): δ 17.13 (-SCH 3 ), 107.53 (- CH=C-), 127.84, 128.96, 132.57, 137.88, (-C 6 H 4 Cl), 167.58 (-C(OH)-), 217.44 (-C=S) ppm.
  10. Yield: (0.266 g, 92%). Anal. Calcd for: C 10 H 9 BrOS 2 (289.21): C 41.53, H 3.14%. Found: C 41.45, H 3.24%. IR (KBr, cm -1 ): = 1117 ( C-OH ), 1584 ( C=C ), 1236 ( C=S ).
  11. H NMR (500.15
  12. MHz, CDCl 3 ): δ 2.66 (s, 3H, -SCH 3 ), 6.90 (s, 1H, -CH=C-), 7.57-7.83 (m, 4H, -C 6 H 4 Br), 15.04 (s, 1H, -C(OH)-) ppm. 13 C{ 1 H} NMR (125.03 MHz, CDCl 3 ): δ 17.33 (-SCH 3 ), 107.69 (- CH=C-), 126.57, 128.17, 129.93, 132.13, (-C 6 H 4 Br), 167.84 (-C(OH)-), 217.73 (-C=S) ppm.
  13. 1=x−1,y,z1 = x-1,y,z 1=x−1,y,z2 -x, y+1/2,-z 3−x+1,y+1/2,−z3 -x+1, y+1/2, -z 3−x+1,y+1/2,−z4 -1+x,1+y,z In 2 1=x−1,y,z1 = x-1,y,z 1=x−1,y,z2 1-x, y-1/2,-3/2-z 3−x,y−1/2,−3/2−z3 -x, y-1/2, -3/2-z 3−x,y−1/2,−3/2−z4 -1+x, -1+y,z In 3 1=½−x,y,½+z1 = ½-x, y, ½+z 1=½−x,y,½+z2 = ½-x, -1+y, ½+z 3=½−x,½−y,z3 = ½-x, ½-y, z 3=½−x,½−y,z4 ½-x, y, z-1/2 5½+x,1−y,3/2−zIn45 ½+x, 1-y,3/2-z In 4 5½+x,1−y,3/2−zIn41 = 1-x, y, z+1/2 2=1−x,y,z−1/22 = 1-x, y, z-1/2 2=1−x,y,z−1/23 = 1-x, 1-y, z 4=1−xy,z−1/24 = 1-x y, z-1/2 4=1−xy,z−1/25 x-1/2, 3/2-y, z In 7b$1= x,y,1+z 2=x−1/2,3/2−y,z2 = x-1/2, 3/2-y, z 2=x−1/2,3/2−y,z3 x-1/2, 3/2-y, 1+z 4−1+x,y,1+z4 -1+x,y,1+z 4−1+x,y,1+z5 x+1/2, 3/2-y, 1+z In 8 1=x1−y,z−1/21 = x 1-y, z-1/2 1=x1−y,z−1/22 x, 1-y, z+1/2 31−x,1−y,z3 1-x, 1-y, z 31−x,1−y,z4 x,1-y,z+1/2
  14. Table S3. Selected bond lengths (Å) and angles (°) for complex 5 S15-Tl1-S15$2 140.09(7) 139.83(7) 89.6(4) S15-Tl1-S16$3 68.14(11) 67.27(12) 110.24(3)
  15. Tl1-S45 3.086(2) Tl2-S45 3.041(2) Symmetry elements 1=2−x,1−y,1−z1 = 2-x, 1-y, 1-z 1=2−x,1−y,1−z2 1-x, 1-y, 1-z $3 1-x,-y,-z Table S4. Selected bond lengths (Å) and angles (°) for complex 6 Tl1-O41 2.848(5) Tl2-S15
  16. Tl1-O11 2.596(10) Tl2-O11 2.732(9) Tl1-S15 3.059(4) Tl2-O41 2.840(12) Tl1-S45$1 3.266(4) Tl2-S45 2.998(3) Symmetry elements 11−x,1−y,z1 1-x, 1-y, z 11−x,1−y,z2 1-x, y-1/2, -z-1/2 3x,−1+y,z3 x, -1+y,z 3x,−1+y,z4 1-x y+1/2, -3/2-z 5x,1+y,z5 x, 1+y, z 5x,1+y,z6 1-x, 2-y, -z
  17. Table S5. Selected bond lengths (Å) and angles (°) for complex 7a Tl1-S15$2
  18. O11-Tl1-S15 64.1(2) O11-Tl2-O41 77.4(3) O11-Tl1-S45$1 86.1(2) O11-Tl2-S45 86.2(2) S15-Tl1-S45$1 92.8(1) O41-Tl2-S45
  19. O51-Tl1-S35$1 63.5(3) O11-Tl2-S35 124.4(3) O31-Tl3- S15$2 65.0(2) O31-Tl1-S35$1 130.9(2) O51$1-Tl2- S35 63.5(3) O11$2-Tl3- S15$2 58.1(2) S35-Tl1-S35$1 77.55(10) S15-Tl2-S35 75.79(10) S55$3-Tl3- S15$2 103.70(10) S55-Tl1-S35$1 106.49(10) S55$1-Tl2- S35 106.79(10) S15-Tl3-S15$2 164.70(19)
  20. O51-Tl1-S36$1 101.4(3) O31-Tl3-S16 168.8(2) O31-Tl1-S36$1 166.4(2) O11$2-Tl3- S16 69.8(2) S35-Tl1-S36$1 107.46(11) S55$3-Tl3-S16 76.26(11) S55-Tl1-S36$1 103.40(11) S15-Tl3-S16 49.65(12) S35$1-Tl1- 48.23(11) S15$2-Tl3-S16 118.53(11) Symmetry Elements 1−x,−y,1−z1 -x, -y, 1-z 1−x,−y,1−z2 x, ½-y, z-1/2 3x,1/2−y,z+1/23 x, 1/2-y, z+1/2 3x,1/2−y,z+1/24 x,y,1+z $5 -x,-y,2-z Table S6. Non-classical hydrogen bonding interactions in 3, 4, 6 and 7b (distances (Å) angles
  21. 62 170 1-x, 1-y, -z C25-H25•••O11 2.61 3.54 167 x-1/2, 1-y, 3/2-z C22-H22•••H25 2.33 2.98 125 x+1/2, 1-y, 3/2-z
  22. * C-H•••CG angle between H•••CG and aromatic ring CG1 is ring C21-C26 inclusive A Symmetry Element C17-H17C•••N24 2.61 3.49 149 3/2-x, 3/2-y, z+1/2
  23. C26-H26•••CG1 2.80 124, 83 * 3/2-x, 3/2-y, z+1/2
  24. Donor (D)•••Acceptor (A) H•••A D•••A D-H•••A Symmetry Element C25-H25C•••F24 2.63 3.22 122 2-x, -y, -z C25-H25•••F54 2.57 3.44 151 2-x, 1-y, -z C55-H55•••F24 2.59 3.16 119 x, 1+y, z Donor (D)•••Acceptor (A) H•••A D•••A D-H•••A Symmetry Element C25A-H25C•••Cl1 2.41 3.33 170 1-x, 2-y, ½+z