VVARIOS ARIOS SSYNTHESIS YNTHESIS MMETHOD OF ETHOD OF

SSUPRAMOLECULAR UPRAMOLECULAR

TTRIANGLERIANGLE FFORMORM

GroupGroup 11. . Dong Hoon Kim, Min Yeong Seol, Jae Min Bak, Jin Taek Choi, Dong Hoon Kim, Min Yeong Seol, Jae Min Bak, Jin Taek Choi,

Nam-Ki Ha, Ho Yun Hwang Nam-Ki Ha, Ho Yun Hwang

DEPARTMENT OF CHEMISTRY, UNIVERSITY OF ULSANDEPARTMENT OF CHEMISTRY, UNIVERSITY OF ULSAN

I. II. INTRODUTIONNTRODUTION

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.

No. 1

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.

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

N

N

F3C

F3C

N

N

CF3

F3C

N

N

CF3

F3C

N N

F3C CF3

M

MM

N

N

N

C3F7

C3F7

N

N N

C3F7

C3F7

N N

NC3F7 C3F7

M

MM

N

N

N

C3F7

C3F7

+acceptor site

Scheme 1. Copper and silver complexes of fluorinated pyrazolates and triazolates

II. EII. EXPERIMENTAL XPERIMENTAL SSECTIONECTION

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).

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 9.

163.5˚ 161.5˚

176.7˚

173.2˚

173.2˚

174.1˚

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

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).

100.63˚

131.08˚

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. EII. EXPERIMENTAL XPERIMENTAL SSECTIONECTION

I I

II

N

Br 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)(NO3)2]stirred at 60 ℃

for 10 min

Scheme 3. Syntheses of ligand 3.

+ [Pd(en)(NO3)2]stirred at 60 ℃

for 10 minin DMSO

1H NMR triangle 4.

1H NMR ligand 1.

Scheme 3. Syntheses of ligand 4.

Figure 4. Data of 1H 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).

11.3 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. EII. EXPERIMENTAL XPERIMENTAL SSECTIONECTION

60◦

• 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

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. EII. EXPERIMENTAL XPERIMENTAL SSECTIONECTION

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(PEt3)2

(NO3)] 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 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 by elemental 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.

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. EII. EXPERIMENTAL XPERIMENTAL SSECTIONECTION

Fig 5. 31P NMR of compound

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 oxygen donor ligands. Attempts to obtain X-ray-quality single crystals of 10 failed.

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.

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

PPh2

PPh2

Pd

OTf

OTfFe 90

◦

N O

O-

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

N

O+Na -OPPh2

PPh2

PdOTf

OTfFe

MeOH, r.t.

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.

PPh2Ph2P

Pd

Fe

N

O

O

N

O

O

PPh2

Ph2P

Pd

Fe

OO

PPh2

Ph2P

Pd

Fe

OO

N

O

3 3+

II. EII. EXPERIMENTAL XPERIMENTAL SSECTIONECTION

3

3

2 1

Figure3. 1H NMR of the triangle

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

PPh2Ph2P

Pd

Fe

N

O

O

N

O

O

PPh2

Ph2P

Pd

Fe

O

O

PPh2

Ph2P

Pd

Fe

O

O

N

O

1 1:

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 characterizationof a unique and unexpected, self-assembled,

supramolecular aggregate formed from platinum 90◦ subunit and rigid pyrazine

Pt

PMe3

OPf

OPf

Me3P90

◦

N

N

180◦

Pyrazine is the smallest, and hence most rigid, lineararomatic linker available for self-assembly processes.

+

Angular Unit (A)

Square (A24 L2

4)

90°

Linear Unit (L)

No. 7

Scheme1. Formation of self-assembled triangle from rigid subunits .

Figure1. PLUTON plot of supramolecular triangle

Pt

PMe3

OPf

OPf

Me3P +

N

NNitromethane

5 min, r.t., 93%

N N PtPt PMe3

PMe3

N

PMe3

Me3P

N

N N

Pt

PMe3Me3P

6+

6 CF3SO3-

+

Angular Unit (A)

90°

Linear Unit (L)Triangle (A2

3 L23)

81.9◦

0.7nm

179◦

-OPf = triflate = CF3SO3-

Yield=93%

II. EII. EXPERIMENTAL XPERIMENTAL SSECTIONECTION

167◦

3 3

1H NMR

31P{1H} NMR

1H NMR (CD3NO2 , 300 MHz): δ=9.41 (s, 2H;Hpyr), 1.79 (d, JP,H.=11.4 Hz, 9H; P-CH3).

31P{1H} NMR(CD3NO2 , 121 MHz): δ = -25.6 (s, 195Pt, satellites, J Pt, P=3269 Hz)

19F NMR19F NMR (CD3NO2 , 282 MHz): δ = -78.1

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).

N N PtPt PMe3

PMe3

N

PMe3

Me3P

N

N N

PtPMe3Me3P

6+

6 CF3SO3-