Transcript 슬라이드 1

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
DEPARTMENT OF CHEMISTRY, UNIVERSITY OF ULSAN
I. I N T R O D U T I O N
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 πarene/π-arene contacts.
II. E X P E R I M E N TA L S E C T I O N
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.
F3C
CF3
F 3C
N
M
N
N
N
N
CF3
F3C
N
M
M
N
N
F 3C
+
Metal(I) oxides
CF3
F3C
C 3F 7
C3F7
C3F7
acceptor site
N
N
N
N
N
N
N
N
N
C3F7
C3F7
M
M
C 3F 7
donor site
M
N
N
C3F7
C3F7
Scheme 1.
Copper and silver complexes of fluorinated pyrazolates and triazolates
N
N 3.
N 1. Cu 1. N 8.
N 9.
N 3.
N 1.
Ag 1. N 8.
N 9.
161.5˚
163.5˚
N 7.
N 2.
N 2.
N 7.
173.2˚
176.7˚
Cu 2.
173.2˚
N 4.
Cu 3.
N 5.
N 6.
Ag 2.
Ag 3.
174.1˚
N 4.
N 5.
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),Cu3N51.871(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).
Figure 3. Extended structures of [Tol][Cu3][Tol ](left) and [Tol][Ag3][Tol](right).
H atoms and C3F7 groups have been omitted for clarity.
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), Cu2P2 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); Ag1N1 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-Ag1P1 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.
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.
II. E X P E R I M E N TA L S E C T I O N
I
I
1,4-diiodobenzene
Negishi coupling
+
Br
1,4-bis(3-pyridyl)benzene
N
I
I
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
Scheme 3. Syntheses of ligand 3.
[Pd(en)(NO3)2]
+
[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 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).
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).
II. E X P E R I M E N TA L S E C T I O N
* Acceptor (60°)
* Donor (180°)
60
◦
Scheme 1. Synthesis of 60° Tecton 3
Scheme 3. Self-Assembly of Supramolecular Triangles
• 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 ◦
• The expected hexanuclear
assembly crystallizes as a
somewhat distorted
triangular species (Figure 2).
• The sides of the triangle are
Figure 2. ORTEP representation (left) and CPK model (right)
2.7 nm in length, and the
based on the X-ray structure of 7. Nitrate anions are omitted
internal cavity is approfor clarity.
ximately one-half that size
(1.4 nm).
No. 4
II. E X P E R I M E N TA L S E C T I O N
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).
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)
60◦
Fig 1. 2,9-bis[trans-Pt(PEt3)2
(NO3)] phenanthrene
ditopic donor
(2)
Fig 2. Oxocarbon Dianion
Scheme 1. Synthesis of 60◦ Tecton 3
Fig 3. ORTEP representation of 3.
Hydrogens are omitted for clarity.
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.
II. E X P E R I M E N TA L S E C T I O N
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).
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.
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
PPh2
90
Fe
OTf
◦
Pd
OTf
PPh2
Square planar Pd(II) has long been among the
favorite metal ions used in coordination-driven selfassembly because of the their rigid coordination
environment and thus it is easy to control the shape
of the final structures.
100◦ angular ditopic donor
N
O
100
◦
nicotinate
O-
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.
II. E X P E R I M E N TA L S E C T I O N
Fe
N
3
Ph2P
Pd
PPh2
O
O
OTf
MeOH, r.t.
Scheme1.
Synthesis of
the triangle
N
Fe
Na -O
O
3
+
OTf
Pd
PPh2
PPh2
O
N
O
O
O
O
O
N
1.3nm
88.2
PPh2
Ph2P
PPh2
0.8nm
Pd
Pd
Ph2P
O
Fe
Fe
◦
3
2
Figure1. ORTEP view of the triangle
with atom numbering
+
3
1
Scheme2. Possible triangular linkage isomers
from a [3 + 3] combination of a 90◦ acceptor
and an ambidentate ligand.
1 : 1
Fe
Figure2. 31P{1H} NMR of the triangle
and the starting material(right).
Ph2P
PPh2
Pd
O
O
N
O
N
O
O
O
O
O
Fe
Figure3. 1H NMR of the triangle
O
N
PPh2
Pd
Pd
Ph2P
PPh2
Ph2P
Fe
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
PMe3
Me3P
Pt
OPf
90
◦
90°
OPf
180◦ ditopic donor
N
180
N
Platinum corner , with its two bonding sites oriented
◦
approximately 90 to one another, is also quite
compact.
+
◦
Angular
Unit (A)
Linear
Unit (L)
Square (A24 L24)
Pyrazine is the smallest, and hence most rigid, linear
aromatic linker available for self-assembly processes.
II. E X P E R I M E N TA L S E C T I O N
6+
PMe3
PMe3
Me3P
PMe3
N
Pt
N
Pt
PMe3
N
Nitromethane
5 min, r.t., 93%
3 Me3P Pt OPf + 3
OPf
N
N
N
N
-OPf = triflate = CF3SO3-
N
6 CF3SO3-
Pt
Me3P
PMe3
Yield=93%
Scheme1. Formation of self-assembled triangle
from rigid subunits .
0.7nm
167
81.9
◦
◦
179
+
◦
90°
Angular
Unit (A)
Figure1. PLUTON plot of supramolecular triangle
Linear
Unit (L)
Triangle (A23 L23)
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).
6+
N
Me3P Pt
31P{1H}
NMR
PMe3
PMe3
N
N
Pt
PMe3
N
31P{1H}
NMR(CD3NO2 , 121 MHz):
δ = -25.6 (s, 195Pt, satellites, J Pt, P=3269 Hz)
19F
19F
N
NMR
NMR (CD3NO2 , 282 MHz): δ = -78.1
N
Pt
Me3P
PMe3
6 CF3SO3-