8.64 (s, 16H, β-Py-H), 2.90 (m, 16H, CO2CH2), 2.30–2.12 (m, 96H, P-CH2-CH3),
1.61 (m, 16H, CH2), 1.50–1.36 (m, 144H, P-CH2-CH3), 1.22 (m, 16H, CH2), −2.97
(br, 4H, NH). 31P{1H}NMR (acetone-d6, 121.4 MHz): δ = 7.43 (d, 2Jp-p = 21.4 Hz,
occurring upon self-assembly. Although the absorption and
emission behaviors are maintained, the solubilities of the prisms
is enhanced relative to the free porphyrins, indicating that such
self-assembly schemes are promising for optimizing the proper-
ties of new light-harvesting materials.
195Pt satellites, 1Jpt-p = 3,282 Hz), 1.67 (2Jp-p = 21.4 Hz, 195Pt satellites, 1Jpt-p
3,373 Hz). ESI-MS (C213H340F15N16O31P16Pt8S5) m/z: [M-3OTf]3+ 2,040.45.
=
Synthesis and Characterization of 5a. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (5.73 mg, 7.85 mmol), potassium tert-phthalate (0.95 mg,
3.93 mmol), Zn-3 (1.34 mg, 1.96 mmol), and 2 mL of solvent. Compound 5a
was obtained as purple solid (6.2 mg, 95%). 1H NMR (300 MHz, acetone-d6):
δ = 9.36 (m, 16H, α-Py-H), 9.15 (s, 8H, pyrrole-H), 8.35 (m, 16H, β-Py-H), 8.09
(s, 16H, phenyl-H), 7.13 (s, 8H, pyrrole-H), 2.41–2.17 (m, 96H, P-CH2-CH3), 1.58–
1.40 (m, 144H, P-CH2-CH3). 31P{1H}NMR (acetone-d6, 121.4 MHz): δ = 7.56
Materials and Methods
cis-Pt(PEt3)2(OTf)2 (1) was prepared according to literature procedures (23).
Dicarboxylic ligand 2 was prepared by neutralization of the corresponding
acid with 2 eq of NaOH or KOH. All other compounds were used as bought
from Sigma-Aldrich, whereas deuterated solvents were purchased from Cam-
bridge Isotope Laboratory. 1H and 31P{1H} spectra were recorded on a Varian
300 spectrometer and the mass spectra were recorded on a Micromass LCT
Premier XE TOF mass spectrometer using ESI and analyzed using the MassLynx
software suite. The ESI-MS samples were dissolved in acetone. All 31P{1H}
spectra were referenced using a 10% (wt/vol) H3PO4 aqueous solution.
(d, 2Jp-p = 20.8 Hz, 195Pt satellites, 1Jpt-p = 3,245 Hz), 2.62 (2Jp-p = 21.4 Hz, 195Pt
1
satellites, Jpt-p
= 3,463 Hz). ESI-MS (C216H304F24N16O40P16Pt8S8Zn2) m/z:
[M-3OTf]3+ 2,072.33, [M-4OTf]4+ 1,516.35.
Synthesis and Characterization of 5b. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (4.03 mg, 5.52 mmol), sodium iso-phthalate (0.60 mg,
2.86 mmol), 3 (0.94 mg, 1.38 mmol), and 1 mL of solvent. Compound 5b was
obtained as purple solid (4.1 mg, 90%). 1H NMR (300 MHz, acetone-d6): δ =
9.36 (m, 16H, α-Py-H), 9.21 (s, 8H, pyrrole-H), 8.96 (s, 4H, Ph-H), 8.36 (d, 16H,
J = 5.7 Hz, β-Py-H), 8.12 (d, 8H, J = 6.7 Hz, phenyl-H), 7.76 (s, 8H, pyrrole-H),
7.32 (t, 4H, J = 7.5 Hz, phenyl-H), 2.39–2.12 (m, 96H, P-CH2-CH3), 1.57–1.41
(m, 144H, P-CH2-CH3). 31P{1H}NMR (acetone-d6, 121.4 MHz): δ = 8.77 (d,
General Procedure for Multicompound Self-Assembly 4 and 5. To a 2-dram vial,
cis-Pt(PEt3)2(OTf)2 (1) (4 eq), dicarboxylate ligand (2) (2 eq), and 5,10,15,20-
tetrakis-(4-pyridyl)-21,23H-porphyrin (3) (1 eq) were placed, and the mixed
solvent of MeCN/MeNO2/CH2Cl2 (1:1:1) was added. The mixture was stirred
at 60 °C for overnight, and the resulting mixture was cooled and filtered.
The multicomponent self-assembly products were isolated via precipitation
by additions of diethyl ether into the concentrated filtrate.
1
2Jp-p = 21.4 Hz, 195Pt satellites, Jpt-p = 3,264 Hz), 2.65 (2Jp-p = 20.8 Hz, 195Pt
Synthesis and Characterization of 4a. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (4.11 mg, 5.64 mmol), potassium tert-phthalate (0.77 mg,
3.67 mmol), 3 (0.88 mg, 1.38 mmol), and 1 mL of solvent. Compound 4a was
obtained as reddish-brown solid (4.2 mg, 93%). 1H NMR (300 MHz, acetone-d6):
δ = 9.38 (d, 16H, J = 4.1 Hz, α-Py-H), 9.31 (s, 8H, pyrrole-H), 8.41 (d, 16H,
J = 4.1 Hz, β-Py-H), 8.07 (s, 16H, phenyl-H), 7.06 (s, 8H, pyrrole-H), 2.41–2.19
(m, 96H, P-CH2-CH3), 1.57–1.40 (m, 144H, P-CH2-CH3), −3.30 (br, 4H, NH).
31P{1H}NMR (acetone-d6, 121.4 MHz): δ = 7.68 (d, 2Jp-p = 21.0 Hz, 195Pt satellites,
1Jpt-p = 3,281 Hz), 2.72 (2Jp-p = 21.0 Hz, 195Pt satellites, 1Jpt-p = 3,682 Hz). ESI-MS
(C213H308F15N16O31P16Pt8S5) m/z: [M-3OTf]3+ 2,030.12.
1
satellites, Jpt-p = 3,440 Hz). ESI-MS (C216H304F24N16O40P16Pt8S8Zn2) m/z:
[M-3OTf]3+ 2,072.32, [M-4OTf]4+ 1,516.85.
Synthesis and Characterization of 5c. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (4.28 mg, 5.87 mmol), potassium hexanedioate (0.65 mg,
2.94 mmol), Zn-3 (1.00 mg, 1.47 mmol), and 1 mL of solvent. Compound 5c
was obtained as purple solid (4.4 mg, 90%). 1H NMR (300 MHz, acetone-d6):
δ = 9.26 (m, 16H, α-Py-H), 9.19 (s, 8H, pyrrole-H), 8.48 (d, 16H, J = 5.4 Hz, β-Py-H),
8.37 (s, 8H, pyrrole-H), 2.80 (br, 16H, CO2CH2), 2.29–2.15 (m, 96H, P-CH2-CH3),
1.63 (s, 16H, CH2), 1.50–1.35 (m, 144H, P-CH2-CH3). 31P{1H}NMR (acetone-d6,
2
121.4 MHz): δ = 7.82 (d, Jp-p = 20.8 Hz, 195Pt satellites, 1Jpt-p = 3,283 Hz),
Synthesis and Characterization of 4b. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (7.88 mg, 10.81 mmol), sodium iso-phthalate (1.14 mg,
5.44 mmol), 3 (1.96 mg, 2.72 mmol), and 2 mL of solvent. Compound 4b was
obtained as reddish-brown solid (8.2 mg, 94%). 1H NMR (300 MHz, acetone-d6):
δ = 9.40 (s, 16H, α-Py-H), 9.34 (s, 8H, pyrrole-H), 8.91 (s, 4H, Ph-H), 8.43
(s, 16H, β-Py-H), 8.12 (d, 8H, J = 6.7 Hz, phenyl-H), 7.74 (s, 8H, pyrrole-H), 7.33 (t,
4H, J = 6.5 Hz, phenyl-H), 2.35–2.21 (m, 96H, P-CH2-CH3), 1.48 (m, 144H, P-CH2-
1
1.88 (2Jp-p = 20.8 Hz, 195Pt satellites, Jpt-p = 3,368 Hz). ESI-MS (C208H320
F
-
24N16O40P16Pt8S8Zn2) m/z: [M-3OTf]3+ 2,045.39, [M-4OTf]4+ 1,497.38.
Synthesis and Characterization of 5d. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (7.44 mg, 10.20 mmol), potassium heptanedioate (1.21 mg, 5.12
mmol), Zn-3 (1.74 mg, 2.55 mmol), and 2 mL of solvent. Compound 5d was
obtained as purple solid (7.7 mg, 91%). 1H NMR (300 MHz, acetone-d6): δ = 9.29
(m, 16H, α-Py-H), 9.15 (s, 8H, pyrrole-H), 8.65 (s, 8H, pyrrole-H), 8.52 (d, 16H, J =
5.4 Hz, β-Py-H,), 2.80 (br, 16H, CO2CH2), 2.26–2.10 (m, 96H, P-CH2-CH3), 1.66
(m, 24H, CH2), 1.49–1.34 (m, 144H, P-CH2-CH3). 31P{1H}NMR (acetone-d6, 121.4
CH3), −3.29 (br, 4H, NH). 31P{1H}NMR (acetone-d6, 121.4 MHz): δ = 8.85 (d, 2Jp-p
=
21.1 Hz, 195Pt satellites, 1Jpt-p = 3,258 Hz), 2.70 (2Jp-p = 21.1 Hz, 195Pt satellites,
1Jpt-p = 3,440 Hz). ESI-MS (C213H308F15N16O31P16Pt8S5) m/z: [M-3OTf]3+ 2,029.91.
MHz): δ = 7.68 (d, 2Jp-p = 21.4 Hz, 195Pt satellites, 1Jpt-p = 3,248 Hz), 1.67 (2Jp-p
=
Synthesis and Characterization of 4c. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (9.22 mg, 12.65 mmol), potassium hexanedioate (1.30 mg,
6.19 mmol), 3 (2.01 mg, 3.16 mmol), and 2 mL of solvent. Compound 4c was
obtained as reddish-brown solid (9.2 mg, 90%). 1H NMR (300 MHz, acetone-d6):
δ = 9.38 (s, 8H, pyrrole-H), 9.33 (m, 16H, α-Py-H), 8.58 (d, 16H, J = 5.4 Hz,
β-Py-H), 8.35 (s, 8H, pyrrole-H), 2.88 (br, 16H, CO2CH2), 2.30–2.10 (m, 96H,
P-CH2-CH3), 1.64 (s, 16H, CH2), 1.52–1.36 (m, 144H, P-CH2-CH3), −3.01 (br, 4H,
21.4 Hz, 195Pt satellites, 1Jpt-p = 3,404 Hz). ESI-MS (C212H328F24N16O40P16Pt8S8Zn2)
m/z: [M-3OTf]3+ 2,064.41, [M-4OTf]4+ 1,511.42.
Synthesis and Characterization of 5e. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (6.18 mg, 8.47 mmol), potassium octanedioate (1.06 mg,
4.23 mmol), Zn-3 (1.43 mg, 2.10 mmol), and 2 mL of solvent. Compound 5e
was obtained as purple solid (6.54 mg, 93%). 1H NMR (300 MHz, acetone-d6):
δ = 9.27 (br, 16H, α-Py-H), 9.12 (s, 8H, pyrrole-H), 8.74 (s, 8H, pyrrole-H,), 8.54
(d, 16H, J = 5.4 Hz, β-Py-H), 2.80 (m, 16H, CO2CH2), 2.31–2.09 (m, 96H, P-CH2-CH3),
1.57 (m, 16H, CH2), 1.48–1.33 (m, 144H, P-CH2-CH3), 1.23 (m, 16H, CH2).
31P{1H}NMR (acetone-d6, 121.4 MHz): δ = 7.37 (d, 2Jp-p = 20.8 Hz, 195Pt satellites,
1Jpt-p = 3,253 Hz), 1.70 (2Jp-p = 20.8 Hz, 195Pt satellites, 1Jpt-p = 3,392 Hz). ESI-MS
(C216H336F24N16O40P16Pt8S8Zn2) m/z: [M-3OTf]3+ 2,083.41, [M-4OTf]4+ 1,525.43.
2
NH). 31P{1H}NMR (acetone-d6, 121.4 MHz): δ = 7.90 (d, Jp-p = 21.0 Hz, 195Pt
satellites, 1Jpt-p = 3,288 Hz), 1.91 (2Jp-p = 21.0 Hz, 195Pt satellites, 1Jpt-p = 3,392
Hz). ESI-MS (C205H324F15N16O31P16Pt8S5) m/z: [M-3OTf]3+ 2,003.41.
Synthesis and Characterization of 4d. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (8.37 mg, 11.98 mmol), potassium heptanedioate (1.29 mg,
6.09 mmol), 3 (1.95 mg, 3.06 mmol), and 2 mL of solvent. Compound 4d was
obtained as reddish-brown solid (8.8 mg, 91%). 1H NMR (300 MHz, acetone-d6):
δ = 9.38 (m, 16H, α-Py-H), 9.32 (s, 8H, pyrrole-H), 8.61 (m, 24H, β-Py-H,
pyrrole-H), 2.89 (br, 16H, CO2CH2), 2.29–2.13 (m, 96H, P-CH2-CH3), 1.69 (m,
24H, CH2), 1.51–1.36 (m, 144H, P-CH2-CH3), −2.98 (br, 4H, NH). 31P{1H}NMR
Spectroscopic Measurements. Absorption and fluorescence spectra were recorded
on a Hitachi U-4100 and Hitachi F-7000 Spectrophotometer, respectively, with
aerated spectroscopic-grade DCM, acetone, and DMSO (Sigma-Aldrich) at room
temperature. The cells used in the experiments were 1-cm quartz cuvettes from
Starna Cells. All samples were freshly prepared for each measurement. The ex-
tinction coefficients were determined by preparing four samples ranging in
absorption from 0.01 to 1.0 with concentrations of 0.3–2.0 μM. The molar ab-
sorptivities for each solution were then calculated using Beer’s Law, and the four
were averaged. Subsequent samples were then prepared to confirm the ex-
tinction coefficients. The fluorescence quantum yield for 4 was calculated using
rhodamine 6G standard (Φ = 0.88 in ethanol) (63), and the fluorescence quan-
tum yield for 5 was calculated using rhodamine B (Φ = 0.50 in ethanol) (64).
2
1
(acetone-d6, 121.4 MHz): δ = 7.73 (d, Jp-p = 21.4 Hz, 195Pt satellites, Jpt-p
=
3,237 Hz), 1.67 (2Jp-p = 21.4 Hz, 195Pt satellites, 1Jpt-p = 3,360 Hz). ESI-MS
(C209H332F15N16O31P16Pt8S5) m/z: [M-3OTf]3+ 2,022.12.
Synthesis and Characterization of 4e. Reaction scale was as follows: cis-Pt
(PEt3)2(OTf)2 (1) (8.75 mg, 12.02 mmol), potassium octanedioate (1.31 mg,
6.11 mmol), 3 (1.94 mg, 3.06 mmol), and 2 mL of solvent. Compound 4e was
obtained as reddish-brown solid (9.0 mg, 91%). 1H NMR (300 MHz, acetone-d6):
δ = 9.39 (br, 16H, α-Py-H), 9.28 (s, 8H, pyrrole-H), 8.73 (s, 8H, pyrrole-H,),
Shi et al.
PNAS Early Edition
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