Crystal and molecular structure of a five-coordinate zinc complex of meso-tetraphenyltetrabenzoprophyrin

Cheng, Richard P.; Chen, Yu-Ren; Wang, S.L.; Cheng, C.Y.

doi:10.1016/s0277-5387(00)84326-0

Cited by 47 publications

(33 citation statements)

References 16 publications

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“…The total out-ofplane distortion (D oop = 2.83 ) is almost exclusively described by saddling (B2u = 2.83 ), while doming (A2u = 0.045 ), wave x and wave y deformations (similar to a chair conformation in cyclohexane, in either the x or y direction; Eg = 0.042 and 0.068 , respectively), propellering (A1u = 0.0003 ), and ruffling (B1u = 0.006 ) contribute only slightly to the nonplanarity. This distortion is greater than that found in [Zn(tpbp)] (D oop = 2.35 ), [25] yet is less than that of a [Ni(tpbp(CO 2 Me) 8 )] derivative (D oop = 3.43 ). [23] Electrochemical analysis of [Pt(tpbp)], versus an internal ferrocene reference, shows a reversible oxidation at 0.24 V and quasireversible reduction at À1.85 V. The highest occupied (HOMO) and the lowest unoccupied (LUMO) molecular orbitals calculated from these data are 4.9 and 2.5 eV in energy relative to vacuum, respectively.…”

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confidence: 59%

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Highly Efficient, Near‐Infrared Electrophosphorescence from a Pt–Metalloporphyrin Complex

et al. 2007

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Organic light-emitting diodes (OLEDs) have been the subject of a significant research effort for the past two decades with a focus on devices that emit almost exclusively in the visible part of the electromagnetic spectrum.[1] Recently, there has been a growing interest in OLEDs that emit in the nearinfrared (NIR) region (700-2500 nm). [2][3][4] Applications for these NIR OLEDs are particularly interesting for nightvision-readable displays [5] and sensors.[6] The efficiency of OLEDs are markedly improved when fluorescent emissive dopants are replaced with phosphorescent heavy-metal complexes that can effectively harvest both the singlet and triplet excitons formed in electroluminescence, with wavelengths (l) ranging from the near-ultraviolet into the red (with peak emission at l max = 380-650 nm).[7-10] Herein, we report on an efficient NIR OLED that utilizes a phosphorescent Ptmetalloporphyrin dopant, with an external quantum efficiency (EQE) greater than 6 % at l max = 765 nm and a full width at half maximum of 31 nm (500 cm À1 ). Previously, two classes of phosphorescent complexes have been employed as dopants in NIR-emitting OLEDs. The first utilizes trivalent lanthanide cations (Ln 3+ ) as the emitting centers, for example, Er 3+ or Nd 3+ , chelated with chromophoric ligands to sensitize excitation-energy transfer to the lanthanide ion.[11] Schanze et al. have reported an NIR OLED utilizing Ln 3+ in conjunction with a porphyrin/polystyrene matrix, with EQE ranging from 8.0 10 À4 to 2.0 10 À4 % at approximately 1 mA cm À2 . [5] Similarly, a Nd(phenalenone) 3 -based OLED had an EQE of 0.007 % at l max = 1065 nm.[4] The second class of NIR OLEDs is transition-metal complexes, similar to those used in the visible region. A recent report of an electrophosphorescent device that used a cyclometalated [(pyrenyl-quinolyl) 2 Ir(acac)] complex as the phosphor gave l max = 720 nm and an EQE of 0.1 %. [6] A family of complexes that have shown intense absorption and emission in the red-to-NIR region of the spectrum are the metalloporphyrins. [12,13] There are a number of reports of OLEDs fabricated with [Pt(oep)], [Pt(tpp)] (oep = 2,3,7,8,12,13,17,18-ocatethylporphryin, tpp = 5,10,15,20-tetraphenylporphyrin), or analogues of these compounds as phosphorescent emitters, with emission maxima between 630 and 650 nm, [7,[14][15][16][17][18][19][20][21][22] however, there has been no apparent effort to shift the Pt-porphyrin-based OLED emission into the NIR region. Porphyrin chromophores with fused aromatic moieties at the b-pyrrole positions, for example, tetrabenzoporphyrin (bp), exhibit a bathochromic shift (relative to unsubstituted porphyrin) of the absorption and emission energy, owing to the expansion of the p-electronic system of the porphyrin core.[23] The addition of bulky groups to the meso positions of the porphyrin macrocycles with b-substituted pyrroles leads to the formation of nonplanar porphyrins, and further red-shifts the absorption spectra.[24] Coordination of a heavy-metal atom increases the rate of the int...

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confidence: 59%

“…[25] Crystallographic data are available in the Supporting Information and from the Cambridge Crystallographic Data Centre (CCDC-627735).…”

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confidence: 99%

Highly Efficient, Near‐Infrared Electrophosphorescence from a Pt–Metalloporphyrin Complex

et al. 2007

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“…Edge views are shown in Figure 5. In a similar manner to TBTBP, [22] peripheral expansion of the p system with fused benzene rings results in severe saddling in the case of TPS2N2, TPSN3, and 3BN: the plane angles of opposite indole and isothianaphthene moieties were 131.56(6) and 134.40(5)8 in TPS2N2, 128.70 (7) and 138.00(4)8 in TPSN3, and 136.68(6) and 143.62 (7)8 in 3BN. The most striking feature is the distortion of the benzo rings observed in the isothianaphthene moieties of 2BS.…”

Section: Wwwchemeurjorgmentioning

confidence: 97%

“…TBP, SN3, S2N2, OSN2, ON3, TPTBP, TPSN3, TPS2N2, CSN2, CN3, 3BN, 2BS, 2BN, and 1BS with carbon numbering schemes. [22] The pathway of the dominant ring current observed on the basis of NMR spectroscopy is shown in bold.…”

Section: Introductionmentioning

confidence: 99%

Application of MCD Spectroscopy and TD‐DFT to Nonplanar Core‐Modified Tetrabenzoporphyrins: Effect of Reduced Symmetry on Nonplanar Porphyrinoids

Mack

Bunya

Shimizu

et al. 2008

Chemistry A European J

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The optical spectra of a series of core-modified tetrabenzoporphyrins were analyzed to determine the effects of core modification, ligand folding, and partial benzo substitution at the ligand periphery on the electronic structure by using magnetic circular dichroism (MCD) and NMR spectroscopy, X-ray crystallography, cyclic and differential pulse voltammetry, and TD-DFT calculations. Planar 21-carba-, 21-thia-, 21,23-dithia-, and 21-oxa-23-thiatetrabenzo[b,g,l,q]porphyrins reported previously were studied together with the previously unreported 21-oxa- and 21-carba-23-thiatetrabenzo[b,g,l,q]porphyrins. The optical properties of these compounds are compared to those of tetrabenzo[b,g,l,q]-, 5,10,15,20-tetraphenyl-, 5,10,15,20-tetraphenyltetrabenzo[b,g,l,q]-21-thia-, 5,10,15,20-tetraphenyltetrabenzodithia-, 5,10,15,20-tetraphenyldibenzo[g,q]-21,23-dithia-, 5,10,15,20-tetraphenyldibenzo[b,l]-21,23-dithia-, 5,10,15,20-tetraphenyltribenzo[g,q,l]-21-thia-, and 5,10,15,20-tetraphenylbenzo[b]-21-thiaporphyrins. Michl's perimeter model and Gouterman's four-orbital model are used to conceptualize the results and to account for red shifts commonly observed in the spectral bands of nonplanar porphyrinoids.

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“…[7] Увеличение реакционной способности комплекса 1 с NiCl 2 в ДМФА по сравнению с тетрабензопорфиринатом Сd(II) можно объ-яснить изменением геометрии молекулы при введении объемных фенильных заместителей. В работе [10] полу-чены рентгеноструктурные данные для комплекса Zn(II) c порфирином 1. Показано, что порфиринат Zn(II) нахо-дится в седлообразной конформации со средним откло-нением С β -атомов молекулы от исходной плоскости макрокольца ДС β =0.765 Å.…”

Section: результаты и обсуждениеunclassified

Tetraphenyltetrabenzoporphyrinates of Ni(II), Pd(II), Pt(II) and Pt(IV)

Maltceva¹,

Чижова²,

Kumeev³

et al. 2017

MHC

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Crystal and molecular structure of a five-coordinate zinc complex of meso-tetraphenyltetrabenzoprophyrin

Cited by 47 publications

References 16 publications

Highly Efficient, Near‐Infrared Electrophosphorescence from a Pt–Metalloporphyrin Complex

Highly Efficient, Near‐Infrared Electrophosphorescence from a Pt–Metalloporphyrin Complex

Application of MCD Spectroscopy and TD‐DFT to Nonplanar Core‐Modified Tetrabenzoporphyrins: Effect of Reduced Symmetry on Nonplanar Porphyrinoids

Tetraphenyltetrabenzoporphyrinates of Ni(II), Pd(II), Pt(II) and Pt(IV)

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