Interpretation of the Near-Infrared Absorption of Magnesium Phthalocyanine Complexes in Terms of Exciton Coupling Effects

Endo, Akira; Matsumoto, Shinya; Mizuguchi, Jin

doi:10.1021/jp991624y

Cited by 83 publications

(71 citation statements)

References 20 publications

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“…MgPc is known to accommodate water and/or solvent molecules upon crystallization [4][5][6]. Thus, the electronic spectra vary significantly due to intermolecular interactions in the molecular arrangement [7]. The present structure analysis has been carried out in order to study the correlation between crystal and electronic structures in MgPc complexes.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of aquamagnesiumphthalocyanine pyridine (2/3), 2(C32H16N8)Mg(H2O) · 3C5H5N

Mizuguchi

Mochizuki

2002

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialMagnesiumphthalocyanine was purchased from Aldrich Chemical Industry Inc. The product was purified once by sublimation. using a two-zone furnace [1]. The single crystals were then grown from solution in pyridine by solvent evaporation at room temperature. DiscussionMagnesiumphthalocyanine (MgPc) is a blue pigment and used also as a photocoonductor for laser printers [2,3]. MgPc is known to accommodate water and/or solvent molecules upon crystallization [4][5][6]. Thus, the electronic spectra vary significantly due to intermolecular interactions in the molecular arrangement [7]. The present structure analysis has been carried out in order to study the correlation between crystal and electronic structures in MgPc complexes. When MgPc was recrystallized from solution in pyridine, two kinds of complexes were obtained: MgPc(H 2 O) · 2(pyridine) and 2(MgPc)(H 2O) · 3(pyridine). The former coincides with the structure reported by Fischer and others [3] while the latter is reported here. The complex is composed of two MgPc molecules arranged in convex pairs together with two water and three pyridine molecules. The O atom of water is coordinated to the central Mg atom of MgPc. The Mg atom is shifted by about 0.45 Å out of the plane of the four nitrogen atoms, forming a pyramidal structure. The electron-rich nitrogen of pyridine is hydrogen-bonded to the water molecule in the N···HO form. This H-bond formation occurs in both MgPc molecules. In addition, the third pyridine molecule exists alongside the hydrogen-bonded pyridine molecule as shown in the figure. However, this pyridine molecule is rather free because no hydrogen bond is recognized between the pyridine and water molecules. The complex molecules are then stacked alternately nearly along the (a,b)-diagonal direction. The essential difference between MgPc(H 2 O) · 2(pyridine) and 2(MgPc)(H 2 O) · 3(pyridine) is that two pyridine molecules are hydrogen-bonded to one water molelcule in the former case while there is only one pyridine molecule in the latter case.

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Section: Discussionmentioning

confidence: 99%

Crystal structure of aquamagnesiumphthalocyanine pyridine (2/3), 2(C32H16N8)Mg(H2O) · 3C5H5N

Mizuguchi

Mochizuki

2002

Zeitschrift Für Kristallographie - New Crystal Structures

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“…We have pointed out in our previous reports [5,10,15,16] that, in organic pigments, the excitonic interactions play an important role in the determination of electronic structure (i.e. color) in the solid state.…”

Section: Assignment Of the Long-wavelength Bandmentioning

confidence: 99%

Polymorph of N,N′-di-n-butylperylene-3,4:9,10-bis(dicarboximide) and their electronic structure

Mizuguchi

2006

Dyes and Pigments

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Perylene pigments are known to exhibit a variety of shades in the solid state from vivid red, via maroon to black, although their solution spectra are quite similar. A second phase of the title compound (phase II) has newly been found when the single crystals were grown from the vapor phase. Phase II bears a black color while the previous phase (phase I) exhibits red-maroon. For this reason, the electronic structure of both phases has been investigated on the basis of the crystal structure as well as intermolecular interactions. In both phases, the absorption spectrum is composed of two bands: one is due to individual molecules (i.e. around 450e550 nm) and the second band arises from excitonic interactions between transition dipoles (i.e. around 600 nm in phase I and 625 nm in phase II). The intermolecular interactions along the stacking axis are primarily responsible for the appearance of the second band in both phases. Additionally, the interaction on the molecular plane is found to be slightly hypsochromic in phase I while bathochromic in phase II. This induces a difference in absorption maximum of the second band, leading to two different colors (red-maroon and black) in phases I and II.

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“…The origin of it is not clearly determined up to now. In one of the papers the broad-band absorption is associated with exciton coupling effects which are the result of energy levels degeneration due to the symmetry lowering from D 4v to C 1 [20]. Another report focuses on the structural aspect of the problem, comparing triclinic and monoclinic modifications of MgPc(H 2 O), of which the first one is active and the second is not [11].…”

Section: Introductionmentioning

confidence: 99%

New near-IR active MgPc(H2O) polymorphic modification: Synthesis, structural investigation, thermal stability and spectroscopy

Kinzhybalo

Janczak

2011

Journal of Molecular Structure

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Interpretation of the Near-Infrared Absorption of Magnesium Phthalocyanine Complexes in Terms of Exciton Coupling Effects

Cited by 83 publications

References 20 publications

Crystal structure of aquamagnesiumphthalocyanine pyridine (2/3), 2(C32H16N8)Mg(H2O) · 3C5H5N

Crystal structure of aquamagnesiumphthalocyanine pyridine (2/3), 2(C32H16N8)Mg(H2O) · 3C5H5N

Polymorph of N,N′-di-n-butylperylene-3,4:9,10-bis(dicarboximide) and their electronic structure

New near-IR active MgPc(H2O) polymorphic modification: Synthesis, structural investigation, thermal stability and spectroscopy

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