V ARIOS S YNTHESIS M ETHOD OF S UPRAMOLECULAR T RIANGLE F ORM V ARIOS S YNTHESIS M ETHOD OF S UPRAMOLECULAR T RIANGLE F ORM Group 1. Dong Hoon Kim, Min Yeong Seol, Jae Min Bak, Jin Taek Choi, Nam-Ki Ha, Ho Yun Hwang Group 1. Dong Hoon Kim, Min Yeong Seol, Jae Min Bak, Jin Taek Choi, Nam-Ki Ha, Ho Yun Hwang DEPARTMENT OF CHEMISTRY, UNIVERSITY OF ULSAN

I. I NTRODUTION

Figure 1. Copper and silver complexes of fluorinated pyrazolates and triazolates, {[3,5-(CF 3 ) 2 Pz]M} 3 and {[3,5-(C 3 F 7 ) 2 Tz]M} 3 (M ) Cu, Ag), showing the trinuclear structure. No. 1 Cu I and Ag I complexes of the fluorinated triazolate ligand [3,5-(C 3 F 7 ) 2 Tz]- have been synthesized using the corresponding metal(I) oxides and the triazole. They form π-acid/base adducts with toluene, leading to [Tol][M 3 ][Tol] ([Tol] ) toluene; [M 3 ] ) {[3,5-(C 3 F 7 ) 2 Tz]Cu} 3 or {[3,5-(C 3 F 7 ) 2 Tz]Ag} 3 ) type structures. Packing diagrams show the presence of extended chains of the type {[Tol][M 3 ][Tol]} ∞, but the intertoluene ring distances are too long for significant π- arene/π-arene contacts.

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. donor site Metal(I) oxides + acceptor site Scheme 1. Copper and silver complexes of fluorinated pyrazolates and triazolates II. E XPERIMENTAL S ECTION

Figure 2. Molecular structures of [(toluene){[3,5-(C 3 F 7 ) 2 Tz]Cu} 3 (toluene)],[Tol][Cu 3 ][Tol] (left), and [(toluene){[3,5-(C 3 F 7 ) 2 Tz]Ag} 3 (toluene)], [Tol]-[Ag 3 ][Tol] (right). H atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg.) : Cu1-N (8), Cu1-N (7), Cu2-N (8),Cu2-N (8),Cu3- N51.871(8),Cu3-N (8),N8-Cu1-N (3), N2-Cu2-N (4), N5-Cu3-N (4); Ag1-N (3), Ag1-N (3), Ag2-N (3), Ag2-N (3), Ag3-N (3), Ag3-N (3), N8-Ag1-N (12), N4-Ag2-N (12), N7-Ag3-N (12). Cu 1. Cu 2.Cu 3. N 1. N 2. N 3. N 4.N 5. N 6. N 7. N 8.N 9. Ag 1. Ag 2.Ag 3. N 1. N 2. N 3. N 4. N 5. N 6. N 7. N 8. N ˚ ˚ ˚ ˚ ˚

Figure 3. Extended structures of [Tol][Cu 3 ][Tol ](left) and [Tol][Ag 3 ][Tol](right). H atoms and C 3 F 7 groups have been omitted for clarity.

Figure 3. Molecular structures of {[3,5-(C 3 F 7 ) 2 Tz]Cu(PPh 3 )} 2 (left) and {[3,5-(C 3 F 7 ) 2 Tz]Ag(PPh 3 )} 2 (right). H atoms have been omitted for clarity. Selected bond lengths (Å) and angles (deg.): Cu1-N (4), Cu1-N (4), Cu1-P (11), Cu2-N (4), Cu2-N (4), Cu2-P (12), N1-Cu1-N (15), N1-Cu1-P (11), N4-Cu1-P (12), N5-Cu2-N (17), N5-Cu2-P (13), N2-Cu2-P (12); Ag1-N (4), Ag1-N (4), Ag1-P (13), Ag1· · ·Ag (5), Ag2-N (4), Ag2-P (13), Ag2-N (5), N1-Ag1-N (15), N1-Ag1-P (12), N4-Ag1-P (11), N2-Ag2-P (12), N2-Ag2-N (16), P2-Ag2-N (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 PPh 3.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.

Figure 4. Palladium complex of 1,4-bis(3-pyridyl)benzene ligands. 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. No. 2

+ II. E XPERIMENTAL S ECTION + Negishi coupling 1,4-bis(3-pyridyl)benzene 4,4’-bis(3-pyridyl)biphenyl Scheme 2. Syntheses of 1,4-Bis(1-pyridyl)benzene and 4,4`-bis(3-pyridyl)biphenyl. 1,4-diiodobenzene 4,4’-diiodobiphenyl 3-bromopyridine [Pd(en)(NO 3 ) 2 ] stirred at 60 ℃ for 10 min Scheme 3. Syntheses of ligand 3.

+ [Pd(en)(NO 3 ) 2 ] stirred at 60 ℃ for 10 min in DMSO 1 H NMR triangle 4. 1 H NMR ligand 1. Scheme 3. Syntheses of ligand 4. Figure 4. Data of 1 H NMR triangle (4) and Ligand 1. Figure 5. Representation of [{Pd(en)} 2 (1) 2 ] 4+ in the crystal structure of 3; palladium (magenta), nitrogen (blue), carbon (gray) Å 2.0 Å

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). No. 3

* Acceptor (60°) * Donor (180°) Scheme 3. Self-Assembly of Supramolecular Triangles Scheme 1. Synthesis of 60° Tecton 3 II. E XPERIMENTAL S ECTION 60 ◦

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

60 ◦ Figure 2. ORTEP representation (left) and CPK model (right) based on the X-ray structure of 7. Nitrate anions are omitted for clarity. 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).

No. 4 II. E XPERIMENTAL S ECTION 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.

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.

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).

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. Platinum-Based Acceptor Linker 60 ◦ Fig 1. 2,9-bis[trans-Pt(PEt 3 ) 2 (NO 3 )] phenanthrene 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. ditopic donor Fig 2. Oxocarbon Dianion (1) (2) Self-Assembly of Neutral Platinum-Based Supramolecular Ensembles Incorporating Oxocarbon Dianions and Oxalate (Triangle) No. 5

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 reaction with AgNO 3. The resulting 2,9-bis[trans-Pt(PEt 3 ) 2 (NO 3 )] phenanthrene 3 was isolated as a clear crystalline compound, stable in air at room temperature. Tecton 3 was analyzed by elemental analysis, 1 H, 13 C{1H}, and 31 P{1H} NMR spectroscopy. Four equivalent phosphorus atoms in the molecule give rise to a sharp singlet at 20 ppm in the 31 P{1H} spectrum, with accompanying 195 Pt satellites. Scheme 1. Synthesis of 60 ◦ Tecton 3 Fig 3. ORTEP representation of 3. Hydrogens are omitted for clarity.

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). II. E XPERIMENTAL S ECTION

Fig P NMR of compound The triangle [1] show the singlet 31 P 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 oxygen donor ligands. Attempts to obtain X-ray-quality single crystals of 10 failed.

Fig 5. 1 H 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.

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 ◦ ditopic Pd(II) acceptor 100 ◦ angular ditopic donor 90 ◦ nicotinate 100 ◦ 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). No. 6 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.

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

Figure3. 1 H NMR of the triangle Figure2. 31 P{ 1 H} NMR of the triangle and the starting material(right). 11 :

Platinum corner, with its two bonding sites oriented approximately 90 ◦ to one another, is also quite compact. 90 ◦ ditopic platinum acceptor 180 ◦ ditopic donor The formation and characterization of a unique and unexpected, self-assembled, supramolecular aggregate formed from platinum 90 ◦ subunit and rigid pyrazine 90 ◦ 180 ◦ Pyrazine is the smallest, and hence most rigid, linear aromatic linker available for self-assembly processes. Angular Unit (A) Square (A 2 4 L 2 4 ) 90° Linear Unit (L) No. 7

Scheme1. Formation of self-assembled triangle from rigid subunits. Figure1. PLUTON plot of supramolecular triangle Angular Unit (A) 90° Linear Unit (L) Triangle (A 2 3 L 2 3 ) 81.9 ◦ 0.7nm 179 ◦ -OPf = triflate = CF 3 SO 3 - Yield=93% II. E XPERIMENTAL S ECTION 167 ◦ 3 3

1 H NMR 31 P{ 1 H} NMR 1 H NMR (CD 3 NO 2, 300 MHz): δ=9.41 (s, 2H;H pyr ), 1.79 (d, J P,H.=11.4 Hz, 9H; P-CH 3 ). 31 P{ 1 H} NMR(CD 3 NO 2, 121 MHz): δ = (s, 195 Pt, satellites, J Pt, P =3269 Hz) 19 F NMR 19 F NMR (CD 3 NO 2, 282 MHz): δ = C{ 1 H} NMR 13 C{ 1 H} NMR (CD 3 NO 2, 75 MHz): δ=151.8 (s, C pyr ), (q, J C, F =319 Hz, OTf), 14.7 (m,P-CH 3 ).