Oxygen quenching of structurally characterized [5,10,15,20-tetra­kis­(4-fluoro-2,6-di­methyl­phen­yl)por­phy­rinato]platinum(II)

The com­pound [5,10,15,20-tetra­kis­(4-fluoro-2,6-di­methyl­phen­yl)por­phy­rinato]platinum(II), [Pt(C₅₂H₄₀F₄N₄)] or Pt(II)TFP, has been synthesized and structurally characterized by single-crystal X-ray crystallography. The Pt por­phy­rin exhibits a long-lived phospho­rescent excited state (τ₀ = 66 µs), which has been characterized by transient absorption and emission spectroscopy. The phos­pho­res­cence is extremely sensitive to oxygen, as reflected by a quenching rate constant of 5.0 × 10⁸ M⁻¹ s⁻¹, and as measured by Stern–Volmer quenching analysis.

Computing details

[5,10,15,20-Tetrakis(4-fluoro-2,6-dimethylphenyl)porphyrinato]platinum(II)

Crystal data

[Pt(C52H40F4N4)]	Dx = 1.224 Mg m^−3
Mr = 991.97	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4/m	Cell parameters from 9892 reflections
a = 17.1883 (13) Å	θ = 2.4–25.0°
c = 9.1123 (9) Å	µ = 2.65 mm^−1
V = 2692.1 (5) Å^3	T = 100 K
Z = 2	Plate, red-orange
F(000) = 988	0.18 × 0.09 × 0.08 mm

Data collection

Bruker D8 goniometer with Photon III C14 area detector diffractometer	1773 reflections with I > 2σ(I)
Radiation source: IµS microfocus tube	Rint = 0.062
ω and phi scans	θmax = 25.1°, θmin = 1.7°
Absorption correction: multi-scan (TWINABS; Krause et al., 2015)	h = −13→14
Tmin = 0.391, Tmax = 0.490	k = 0→20
1785 measured reflections	l = 0→10
1785 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.072	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 3.793P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1785 reflections	Δρmax = 1.22 e Å^−3
85 parameters	Δρmin = −0.73 e Å^−3
0 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on all data will be even larger. All non-H atoms were located in difference-Fourier maps, and then refined anisotropically.

The crystal is non-merohedrol twin, but we have well refined the structure by using reflections in hkl5 format that is created by Cell_Now/Twinabs.

Twin law to convert hkl from first to -0.588 0.804 -0.150 this domain (SHELXL TWIN matrix): 0.806 0.592 0.065 0.037 -0.029 -0.996

The disorder solvent molecules could not be located in the Fourier map and have been masked out using PLATON/SQUEEZE.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Pt1	0.500000	0.500000	0.500000	0.02585 (16)
F1	0.2649 (4)	0.9701 (2)	0.500000	0.0799 (16)
N1	0.3894 (2)	0.5388 (3)	0.500000	0.0240 (9)
C1	0.3230 (3)	0.4934 (3)	0.500000	0.0261 (13)
C2	0.2561 (3)	0.5429 (3)	0.500000	0.0298 (13)
H2	0.203292	0.526706	0.500000	0.036*
C3	0.2815 (3)	0.6174 (4)	0.500000	0.0329 (14)
H3	0.250197	0.662942	0.500000	0.039*
C4	0.3651 (3)	0.6142 (3)	0.500000	0.0257 (13)
C5	0.4126 (3)	0.6804 (3)	0.500000	0.0267 (11)
C6	0.3739 (3)	0.7583 (3)	0.500000	0.0287 (12)
C7	0.3550 (2)	0.7940 (2)	0.3663 (5)	0.0338 (9)
C8	0.3184 (3)	0.8660 (3)	0.3683 (5)	0.0438 (11)
H8	0.305291	0.892013	0.279392	0.053*
C9	0.3009 (4)	0.8998 (4)	0.500000	0.0465 (16)
C10	0.3740 (3)	0.7560 (3)	0.2217 (5)	0.0445 (11)
H10A	0.427249	0.735789	0.224187	0.053*
H10B	0.369299	0.794499	0.142787	0.053*
H10C	0.337609	0.713119	0.204177	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.02198 (17)	0.02198 (17)	0.0336 (3)	0.000	0.000	0.000
F1	0.124 (4)	0.039 (2)	0.076 (3)	0.048 (3)	0.000	0.000
N1	0.023 (2)	0.024 (2)	0.025 (2)	−0.001 (2)	0.000	0.000
C1	0.024 (3)	0.029 (3)	0.025 (3)	−0.003 (2)	0.000	0.000
C2	0.022 (3)	0.030 (3)	0.038 (3)	−0.001 (2)	0.000	0.000
C3	0.027 (3)	0.032 (3)	0.039 (4)	0.004 (3)	0.000	0.000
C4	0.023 (3)	0.026 (3)	0.029 (3)	0.004 (2)	0.000	0.000
C5	0.030 (3)	0.025 (3)	0.025 (3)	0.001 (2)	0.000	0.000
C6	0.028 (3)	0.025 (3)	0.033 (3)	0.001 (2)	0.000	0.000
C7	0.035 (2)	0.032 (2)	0.035 (2)	0.0045 (17)	−0.0033 (19)	0.0055 (18)
C8	0.054 (3)	0.040 (2)	0.037 (3)	0.010 (2)	−0.003 (2)	0.009 (2)
C9	0.051 (4)	0.030 (3)	0.059 (5)	0.014 (3)	0.000	0.000
C10	0.052 (3)	0.047 (2)	0.035 (2)	0.011 (2)	−0.003 (2)	0.003 (2)

Geometric parameters (Å, º)

Pt1—N1^i	2.014 (4)	C3—H3	0.9500
Pt1—N1^ii	2.014 (4)	C4—C5	1.400 (8)
Pt1—N1^iii	2.014 (4)	C5—C6	1.494 (7)
Pt1—N1	2.014 (4)	C6—C7^iv	1.403 (5)
F1—C9	1.358 (7)	C6—C7	1.403 (5)
N1—C4	1.362 (8)	C7—C8	1.389 (6)
N1—C1	1.383 (7)	C7—C10	1.506 (6)
C1—C5^ii	1.391 (8)	C8—C9	1.367 (6)
C1—C2	1.430 (8)	C8—H8	0.9517
C2—C3	1.352 (8)	C10—H10A	0.9800
C2—H2	0.9496	C10—H10B	0.9801
C3—C4	1.437 (8)	C10—H10C	0.9800
N1^i—Pt1—N1^ii	180.0	C1^i—C5—C4	123.3 (5)
N1^i—Pt1—N1^iii	90.0	C1^i—C5—C6	118.8 (5)
N1^ii—Pt1—N1^iii	90.0	C4—C5—C6	117.9 (5)
N1^i—Pt1—N1	89.999 (1)	C7^iv—C6—C7	120.6 (5)
N1^ii—Pt1—N1	90.0	C7^iv—C6—C5	119.7 (2)
N1^iii—Pt1—N1	180.0	C7—C6—C5	119.7 (2)
C4—N1—C1	106.4 (4)	C8—C7—C6	118.9 (4)
C4—N1—Pt1	127.2 (4)	C8—C7—C10	119.7 (4)
C1—N1—Pt1	126.3 (4)	C6—C7—C10	121.3 (3)
N1—C1—C5^ii	126.7 (5)	C9—C8—C7	119.3 (4)
N1—C1—C2	109.1 (5)	C9—C8—H8	119.7
C5^ii—C1—C2	124.1 (5)	C7—C8—H8	121.0
C3—C2—C1	107.7 (5)	F1—C9—C8^iv	118.6 (3)
C3—C2—H2	125.9	F1—C9—C8	118.6 (3)
C1—C2—H2	126.4	C8^iv—C9—C8	122.9 (6)
C2—C3—C4	106.7 (6)	C7—C10—H10A	109.6
C2—C3—H3	126.7	C7—C10—H10B	109.4
C4—C3—H3	126.7	H10A—C10—H10B	109.5
N1—C4—C5	126.4 (5)	C7—C10—H10C	109.3
N1—C4—C3	110.1 (5)	H10A—C10—H10C	109.4
C5—C4—C3	123.5 (5)	H10B—C10—H10C	109.6
C4—N1—C1—C5^ii	180.0	N1—C4—C5—C6	180.0
Pt1—N1—C1—C5^ii	0.0	C3—C4—C5—C6	0.0
C4—N1—C1—C2	0.0	C1^i—C5—C6—C7^iv	−90.8 (5)
Pt1—N1—C1—C2	180.0	C4—C5—C6—C7^iv	89.2 (5)
N1—C1—C2—C3	0.0	C1^i—C5—C6—C7	90.8 (5)
C5^ii—C1—C2—C3	180.0	C4—C5—C6—C7	−89.2 (5)
C1—C2—C3—C4	0.0	C7^iv—C6—C7—C8	0.9 (9)
C1—N1—C4—C5	180.0	C5—C6—C7—C8	179.4 (5)
Pt1—N1—C4—C5	0.0	C7^iv—C6—C7—C10	−179.3 (4)
C1—N1—C4—C3	0.0	C5—C6—C7—C10	−0.8 (8)
Pt1—N1—C4—C3	180.0	C6—C7—C8—C9	−0.7 (8)
C2—C3—C4—N1	0.0	C10—C7—C8—C9	179.5 (5)
C2—C3—C4—C5	180.0	C7—C8—C9—F1	−179.8 (6)
N1—C4—C5—C1^i	0.0	C7—C8—C9—C8^iv	0.6 (11)
C3—C4—C5—C1^i	180.0

Symmetry codes: (i) y, −x+1, −z+1; (ii) −y+1, x, z; (iii) −x+1, −y+1, −z+1; (iv) x, y, −z+1.