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Synthesis of Supramolecular Triangle Forms using Pyrazolates and Triazolates

This paper describes the synthesis of trinuclear copper and silver complexes of fluorinated triazolyl ligands. The complexes exhibit interesting π-acid/base chemistry with π bases like toluene, leading to sandwich molecules. The effect of substituents and different arenes on the π-acid/base adduct structures is currently being investigated.

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Synthesis of Supramolecular Triangle Forms using Pyrazolates and Triazolates

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  1. VARIOS SYNTHESIS METHOD OF SUPRAMOLECULAR TRIANGLEFORM Group1. Dong Hoon Kim, Min Yeong Seol, Jae Min Bak, Jin Taek Choi, Nam-Ki Ha, Ho Yun Hwang DEPARTMENT OF CHEMISTRY, UNIVERSITY OF ULSAN

  2. I. INTRODUTION

  3. No. 1 Figure 1. Copper and silver complexes of fluorinated pyrazolates and triazolates, {[3,5-(CF3)2Pz]M}3 and {[3,5-(C3F7)2Tz]M}3 (M ) Cu, Ag), showing the trinuclear structure. CuI and AgI complexes of the fluorinated triazolate ligand [3,5-(C3F7)2Tz]- have been synthesized using the corresponding metal(I) oxides and the triazole. They form π-acid/base adducts with toluene, leading to [Tol][M3][Tol] ([Tol] ) toluene; [M3] ) {[3,5-(C3F7)2Tz]Cu}3 or {[3,5-(C3F7)2Tz]Ag}3) type structures. Packing diagrams show the presence of extended chains of the type {[Tol][M3][Tol]}∞, but the intertoluene ring distances are too long for significant π-arene/π-arene contacts.

  4. II. EXPERIMENTAL SECTION Depending on the reaction conditions and the pyrazolyl ring substituents, they form various pyrazolate ligand-bridged aggregates ranging from trimers, tetramers, hexamers to polymers and supramolecular assemblies. + Metal(I) oxides acceptor site donor site Scheme 1. Copper and silver complexes of fluorinated pyrazolates and triazolates

  5. N 3. Cu 1. N 3. Ag 1. 161.5˚ 163.5˚ N 1. N 8. N 9. N 1. N 8. N 9. 173.2˚ 176.7˚ N 2. 173.2˚ N 7. N 7. N 2. 174.1˚ Cu 2. Cu 3. Ag 2. Ag 3. N 4. N 5. N 4. N 5. N 6. N 6. Figure 2. Molecular structures of [(toluene){[3,5-(C3F7)2Tz]Cu}3(toluene)],[Tol][Cu3][Tol] (left), and [(toluene){[3,5-(C3F7)2Tz]Ag}3 (toluene)], [Tol]-[Ag3][Tol] (right). H atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg.) : Cu1-N8 1.878(8), Cu1-N1 1.887(7), Cu2-N2 1.859(8),Cu2-N4 1.862(8),Cu3-N51.871(8),Cu3-N7 1.877(8),N8-Cu1-N1 163.5(3), N2-Cu2-N4 176.7(4), N5-Cu3-N7 173.2(4); Ag1-N8 2.130(3), Ag1-N1 2.139(3), Ag2-N4 2.102(3), Ag2-N2 2.110(3), Ag3-N7 2.116(3), Ag3-N5 2.117(3), N8-Ag1-N1 161.50(12), N4-Ag2-N2 173.23(12), N7-Ag3-N5 174.07(12).

  6. Figure 3. Extended structures of [Tol][Cu3][Tol ](left) and [Tol][Ag3][Tol](right). H atoms and C3F7 groups have been omitted for clarity.

  7. 100.63˚ 131.08˚ Figure 3. Molecular structures of {[3,5-(C3F7)2Tz]Cu(PPh3)} 2 (left) and {[3,5-(C3F7) 2Tz]Ag(PPh3)} 2 (right). H atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg.): Cu1-N1 2.005(4), Cu1-N4 2.013(4), Cu1-P1 2.1765(11), Cu2-N5 1.982(4), Cu2-N2 2.046(4), Cu2-P2 2.1840(12), N1-Cu1-N4 100.63(15), N1-Cu1-P1 131.08(11), N4-Cu1-P1 126.63(12), N5-Cu2-N2 98.02(17), N5-Cu2-P2 141.21(13), N2-Cu2-P2 120.02(12); Ag1-N1 2.255(4), Ag1-N4 2.278(4), Ag1-P1 2.3502(13), Ag1· · ·Ag2 3.3674(5), Ag2-N2 2.195(4), Ag2-P2 2.3503(13), Ag2-N5 2.402(5), N1-Ag1-N4 95.33(15), N1-Ag1-P1 134.22(12), N4-Ag1-P1 129.50(11), N2-Ag2-P2 152.08(12), N2-Ag2-N5 92.15(16), P2-Ag2-N5 115.23(12). This paper describes the syntheses of trinuclear copper and silver complexes of fluorinated triazolyl ligands. They show interesting π-acid/base chemistry with π bases like toluene, leading to sandwich molecules. Dinuclear copper and silver adducts can be obtained using trinuclear precursors and PPh3.We are currently investigating the effect of various substituents and different arenes on the π-acid/base adduct structures. Photophysical properties of coinage metal triazolates are also of interest.

  8. No. 2 The pyridine-appended nonchelating bidentate ligands 1,4-bis(3-pyridyl) -benzene (1) and 4,4’-bis(3-pyridyl) -biphenyl (2) were complexed with a naked PdII ion for the construction of molecular cage compounds. Figure 4. Palladium complex of 1,4-bis(3-pyridyl)benzene ligands.

  9. II. EXPERIMENTAL SECTION + Negishi coupling 1,4-bis(3-pyridyl)benzene 1,4-diiodobenzene 3-bromopyridine 4,4’-diiodobiphenyl 4,4’-bis(3-pyridyl)biphenyl Scheme 2. Syntheses of 1,4-Bis(1-pyridyl)benzene and 4,4`-bis(3-pyridyl)biphenyl. + stirred at 60 ℃ for 10 min [Pd(en)(NO3)2] Scheme 3. Syntheses of ligand 3.

  10. + [Pd(en)(NO3)2] stirred at 60 ℃ for 10 min in DMSO Scheme 3. Syntheses of ligand 4. 1H NMR triangle 4. 2.0 Å 11.3 Å 1H NMR ligand 1. Figure 5. Representation of [{Pd(en)}2(1)2]4+ in the crystal structure of 3; palladium (magenta), nitrogen (blue), carbon (gray). Figure 4. Data of 1H NMR triangle (4) and Ligand 1.

  11. No. 3 • Researches about the synthesis of discrete supramolecular structures have been interested for more than decades. Especially, triangular molecule one of the simplest possible two-dimensional structures has proven to be surprisingly rate. The difficulty in making triangular structure is finding the appropriate corner unit. Some people use 90º corner unit and flexible side units. In that case, however, the product is mixture of triangular molecules and squares. • In this paper, they report the first predesigned, self-assembled triangules utilizing a unique 60º ditopic, metal-containing corner. These entitles are based on the directional-bonding approach and are formed with neither the assistance of templates, nor are they in noticeable equilibrium with other macrocyclic species. In addition to the single-crystal X-ray structural analysis of one of the assemblies, all three triangles are characterized by multinuclear NMR and electrospray ionization mass spectrometry(ESI-MS).

  12. * Acceptor (60°) * Donor (180°) • II. EXPERIMENTAL SECTION 60◦ Scheme 1. Synthesis of 60° Tecton 3 Scheme 3. Self-Assembly of Supramolecular Triangles

  13. The 31P{1H} NMR spectrum of 7 shows a sharp singlet at 14ppm, with accompanying 195Pt satellites, shifted 6 ppm upfield relative to the position of the phosphorus signal of 3. 195Pt

  14. 60◦ • The expected hexanuclear assembly crystallizes as a somewhat distorted triangular species (Figure 2). • The sides of the triangle are 2.7 nm in length, and the internal cavity is appro-ximately one-half that size (1.4 nm). Figure 2. ORTEP representation (left) and CPK model (right) based on the X-ray structure of 7. Nitrate anions are omitted for clarity.

  15. No. 4 • II. EXPERIMENTAL SECTION Addition of an aqueous solution of the linear linkers 2a, respectively, to an acetone solution, containing 1 equiv of the 60° platinum acceptor linker 1, resulted in immediate precipitation of the neutral triangular macrocycles 3a-d, respectively, in 97-99% isolated yield.

  16. The molecular structure of 3a is shown in Figure 1. Crystallographic data and refinement parameters are given in Table 1. The exterior length of triangle 3a is approximately 25.3 Å, while the internal cavity measures approximately 19.5 Å.

  17. Figure2. Packing diagram of 3a along the c axis(left); solvent in the triangular channels are shown in green, while solvent in the hexagonal channels are shown in blue(CPK). Side view of the stacking nature of different sheets(right). ORTEP of triangle 3b with atom numbering (left). Packing nature of 3b; triethyl phosphine, hydrogen, and solvent molecules are omitted for clarity(right).

  18. No. 5 Self-Assembly of Neutral Platinum-Based Supramolecular Ensembles Incorporating Oxocarbon Dianions and Oxalate (Triangle) Self-Assembly The spontaneous and reversible association of molecular species to form larger, more complex supramolecular entities according to the intrinsic information contained in the components. Platinum-Based Acceptor Linker Pt(ll) has long been among the favorite metal ions used in coordination-driven self-assembly because of the their rigid coordination environment and thus it is easy to control the shape of the final structures. (1) ditopic donor (2) 60◦ Fig 1. 2,9-bis[trans-Pt(PEt3)2 (NO3)] phenanthrene Fig 2. Oxocarbon Dianion

  19. Fig 3. ORTEP representation of 3. Hydrogens are omitted for clarity. Scheme 1. Synthesis of 60◦ Tecton 3 The synthesis of metal-containing corner 3 from 2,9-dibromophenanthrene 1 was accomplished in two steps. First, a double oxidative addition of tetrakis(tri-ethylphosphine)-platinum(0) provided the insertion product 2. Next, the bromine atoms of 2 were exchanged for more labile nitrates by reactionwith AgNO3. The resulting 2,9-bis[trans-Pt(PEt3)2(NO3)] phenanthrene 3 was isolated as a clear crystalline compound, stable in air at room temperature. Tecton 3 was analyzed byelemental analysis, 1H, 13C{1H}, and 31P{1H} NMR spectroscopy. Four equivalent phosphorus atoms in the molecule give rise to a sharp singlet at 20 ppm in the 31P{1H} spectrum, with accompanying 195Pt satellites.

  20. II. EXPERIMENTAL SECTION Scheme 2. Self-Assembly of Oxocarbon Dianions with Platinum-Based Acceptor Linker [1] The neutral supramolecular assemblies were synthesized as shown in Schemes 2. Similar treatment of the 60° platinum acceptor unit (1) with linker (2) , respectively, produced the supramolecular triangle [1] in 85-90% yields (Scheme 2).

  21. The triangle [1]show the singlet 31P resonance at 18.1ppm, respectively, compared to 19.4ppm for the 60° unit 1. The smaller upfield shift of the phosphorus signal in comparison to that of bipyridyl-type nitrogen donor ligands can be attributed to the poorer π-acceptor property of the oxygendonor ligands. Attempts to obtain X-ray-quality single crystals of 10 failed. Fig 5. 31P NMR of compound

  22. Fig 5. 1H NMR of compound The formation of discrete platinum-based metallacycles incorporating flexidentate oxocarbon dianions and oxalate by self-assembly are described. The squarate ion and the 60° tecton undergo 3:3 addition to yield molecular triangle 10 as the squarate ion, which, with its various coordination modes, is unable to provide the geometrical requirement for a rhomboid formation.

  23. No. 6 The synthesis and characterization of an unusual, self-assembled, supramolecular triangle formed from a palladium(II) 90◦ acceptor unit and a 100◦ donor nicotinate linker. (without using a linear linker). 90◦ ditopic Pd(II) acceptor Square planar Pd(II) has long been among the favorite metal ions used in coordination-driven self-assembly because of the their rigid coordination environment and thus it is easy to control the shape of the final structures. 90◦ 100◦ angular ditopic donor Non-symmetric/ambidentate bridging ligands may generate a mixture of isomers due to different connectivities, and thus it is difficult to control both the reaction as well as the isolation of the products in pure form. 100◦ nicotinate

  24. II. EXPERIMENTAL SECTION 3 3 Scheme1. Synthesis of the triangle 0.8nm 1.3nm 88.2◦ 2 1 Scheme2. Possible triangular linkage isomers from a [3 + 3] combination of a 90◦ acceptor and an ambidentate ligand. Figure1. ORTEP view of the triangle with atom numbering

  25. Figure2. 31P{1H} NMR of the triangle and the starting material(right). : 1 1 Figure3. 1H NMR of the triangle

  26. No. 7 The formation and characterization of a unique and unexpected, self-assembled, supramolecular aggregate formed from platinum 90◦ subunit and rigid pyrazine 90◦ ditopic platinum acceptor Platinum corner , with its two bonding sites oriented approximately 90◦to one another, is also quite compact. 90◦ 90° Linear Unit (L) Angular Unit (A) Square (A24 L24) 180◦ ditopic donor Pyrazine is the smallest, and hence most rigid, linear aromatic linker available for self-assembly processes. 180◦

  27. II. EXPERIMENTAL SECTION 3 3 -OPf = triflate = CF3SO3- Yield=93% Scheme1. Formation of self-assembled triangle from rigid subunits . 90° 167◦ 0.7nm Linear Unit (L) Angular Unit (A) Triangle (A23 L23) 179◦ 81.9◦ Figure1. PLUTON plot of supramolecular triangle

  28. 1H NMR 1H NMR (CD3NO2 , 300 MHz): δ=9.41 (s, 2H;Hpyr), 1.79 (d, JP,H.=11.4 Hz, 9H; P-CH3). 13C{1H} NMR 13C{1H} NMR (CD3NO2 , 75 MHz): δ=151.8 (s, Cpyr), 122.2 (q, JC, F=319 Hz, OTf), 14.7 (m,P-CH3). 31P{1H} NMR 31P{1H} NMR(CD3NO2 , 121 MHz): δ = -25.6 (s, 195Pt, satellites, J Pt, P=3269 Hz) 19F NMR 19F NMR (CD3NO2 , 282 MHz): δ = -78.1

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