DCM Molecules Research Articles

Transient absorption spectroscopy of a twisted intramolecular charge transfer (TICT) state in a DCM molecule analyzed by isosbestic points

Transient absorption spectroscopy of a twisted intramolecular charge transfer (TICT) state in a DCM molecule analyzed by isosbestic points

Interrogating the Behaviour of a Styryl Dye Interacting with a Mesoscopic 2D-MOF and Its Luminescent Vapochromic Sensing.

In this contribution, we report on the solid-state-photodynamical properties and further applications of a low dimensional composite material composed by the luminescent trans-4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) dye interacting with a two-dimensional-metal organic framework (2D-MOF), Al-ITQ-HB. Three different samples with increasing concentration of DCM are synthesized and characterized. The broad UV-visible absorption spectra of the DCM/Al-ITQ-HB composites reflect the presence of different species of DCM molecules (monomers and aggregates). In contrast, the emission spectra are narrower and exhibit a bathochromic shift upon increasing the DCM concentration, in agreeance with the formation of adsorbed aggregates. Time-resolved picosecond (ps)-experiments reveal multi-exponential behaviors of the excited composites, further confirming the heterogeneous nature of the samples. Remarkably, DCM/Al-ITQ-HB fluorescence is sensitive to vapors of electron donor aromatic amine compounds like aniline, methylaniline, and benzylamine due to a H-bonding-induced electron transfer (ET) process from the analyte to the surface-adsorbed DCM. These findings bring new insights on the photobehavior of a well-known dye when interacting with a 2D-MOF and its possible application in sensing aniline derivatives.

DCM self-trapping by the host deformation in flexible host–guest molecules

The desolvated structure can self-trap the DCM molecules to return to the 1·DCM state via ligand deformation even under weak host–guest interactions. The capture behavior of DCM is mostly due to the flexibility of the ligand.

Photophysical Properties of 4-Dicyanomethylene-2-methyl-6-(p-dimethylamino-styryl)-4H-pyran Revisited: Fluorescence versus Photoisomerization.

Invited for the cover of this issue are Juan Xie, Rémi Métivier and co-workers at Université Paris-Saclay and Università di Bologna. The image depicts the fluorescence of the DCM molecule reported in this manuscript. Read the full text of the article at 10.1002/chem.202002828.

Confinement Effect of Micro- and Mesoporous Materials on the Spectroscopy and Dynamics of a Stilbene Derivative Dye

Micro- and mesoporous silica-based materials are a class of porous supports that can encapsulate different guest molecules. The formation of these hybrid complexes can be associated with significant alteration of the physico-chemical properties of the guests. Here, we report on a photodynamical study of a push–pull molecule, trans-4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), entrapped within faujasite-type zeolites (HY, NaX, and NaY) and MCM-41 in dichloromethane suspensions. The complex formation gives rise to caged monomers and H- and J-aggregates. Steady-state experiments show that the nanoconfinement provokes net blue shifts of both the absorption and emission spectra, which arise from preferential formation of H-aggregates concomitant with a distortion and/or protonation of the DCM structure. The photodynamics of the hybrid complexes are investigated by nano- to picosecond time-resolved emission experiments. The obtained fluorescence lifetimes are 65–99 ps and 350–400 ps for H- and J-aggregates, respectively, while those of monomers are 2.46–3.87 ns. Evidences for the presence of a charge-transfer (CT) process in trapped DCM molecules (monomers and/or aggregates) are observed. The obtained results are of interest in the interpretation of electron-transfer processes, twisting motions of analogues push–pull systems in confined media and understanding photocatalytic mechanisms using this type of host materials.

Magnetic Sponge Behavior via Electronic State Modulations.

A reversible magnetic change in response to external stimuli is a desired function of molecular magnetic materials. The magnetic change induced by a change in the intrinsic spin is significant because the magnetic change is inevitable and could become drastic. In this study, we demonstrate a reversible magnetic change closely associated with electronic state modulations, as well as structural modifications realized by solvation/desolvation cycles of a magnetic sponge. The compound was a D2A-type layered magnet, [{Ru2(O2CPh-2,3,5-Cl3)4}2(TCNQMe2)]·4DCM (1; 2,3,5-Cl3PhCO2- = 2,3,5-trichlorobenzoate; TCNQMe2 = 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane; DCM = dichloromethane), where [Ru2(O2CPh-2,3,5-Cl3)4] ([Ru2II,II]) is an electron donor (D) and TCNQMe2 is an electron acceptor (A). Compound 1 had a one-electron-transferred, charge-ordered state with a [{Ru2II,II}-TCNQMe2•--{Ru2II,III}+] (1e-I) formula. Strong intralayer antiferromagnetic couplings between [Ru2II,II] with S = 1 or [Ru2II,III]+ with S = 3/2 and TCNQMe2•- with S = 1/2, as well as ferromagnetic interlayer interactions, induced long-range ferrimagnetic ordering at Tc = 101 K. Interstitial DCM molecules were located between layers, and these were gradually eliminated under vacuum at 80 °C to form a solvent-free compound (1-dry) without loss of crystallinity. The electronic state of 1-dry thermally fluctuated and eventually provided a charge-disproportionate disordered state, with a [{Ru2}0.5+-TCNQMe21.5--{Ru2II,III}+] (1.5e-I) formula as the ground state. The Tc in 1-dry was 34 K because of the presence of diamagnetic TCNQMe22- in some parts of the framework. A large Tc variation with Δ Tc ≈ 70 K was switchable; switching was achieved by charge-state modulations accompanied by subtle structural modifications in solvation/desolvation treatments.

Synthesis and solvent vapor-induced transformations of crystals of 1D coordination polymers assembled with continuous void space

9,9′-Biacridine (L1) has a three-dimensional structure of perpendicularly connected acridine moieties with two coordination sites at either end of the molecules. Crystallization of L1 with silver(I) salts gives various 1D coordination polymers with structures that depend on the crystallization solvents and counter anions used. We synthesized six complexes: [Ag(L1)]n(BF4)n·2nTHF (1a·THF, THF = tetrahydrofuran), [Ag(L1)]n(ClO4)n·2nTHF (1b·THF), [Ag(L1)(CH3OH)]n(BF4)n·1.5n(furan) (1a·Furan), [Ag(L1)]n(BF4)n·nDCM (1a·DCM, DCM = dichloromethane), [Ag(L1)]n(ClO4)n·nDCM (1b·DCM), and [Ag2(L1)(CF3COO)2]n (1c). We also synthesized crystals of phenazine (L2) complexed with silver(I) cations which featured layered structures with no void space. In the crystals of 1a·THF and 1b·THF, a linear channel structure formed, which was filled with THF molecules; however, 1a·DCM and 1b·DCM featured no continuous channel structure and their void space was filled with DCM molecules. 1a·Furan had a zigzag-shaped channel filled with furan molecules. The crystal structures of the complexes were similar regardless of whether tetrafluoroborate or perchlorate anions were included in the structure. The crystal structure of 1c showed a ladder structure with chains of silver(I) cations and trifluoroacetate anions. A reversible crystal-to-crystal structural transformation was observed between the complexes of 1a·THF and 1a·DCM, which was investigated by single crystal and powder X-ray diffraction measurements. Our measurements suggested that solvent molecules in the crystal structure were replaced together with concerted rotation of the 1D chains of the coordination polymers, occurring when the crystals were exposed to the vapor of a different solvent.

A stimuli-responsive Au(i) complex based on an aminomethylphosphine template: synthesis, crystalline phases and luminescence properties

Herein we report the synthesis of a stimuli-responsive binuclear Au(I) complex based on the 1,5-bis(p-tolyl)-3,7-bis(pyridine-2-yl)-1,5-diaza-3,7-diphosphacyclooctane ligand, which is a novel template for the design of luminescent metal complexes. In the solid state, the complex obtained gives three different crystalline phases, which were characterized by XRD analysis. It was also found that the crystalline phases can be reversibly interconverted by recrystallization or solvent vapour treatment. The emission of these phases varies in the 500–535 nm range. Quite unexpectedly, the emission energy of these phases is mostly determined by the non-covalent interactions of the solvent molecules with the ligand environment, which have nearly no effect on the Au–Au interactions in the chromophoric centre. The complex obtained demonstrates thermo/solvatochromism to display greenish emission in a DCM matrix and blue emission in an acetone matrix at 77 K, in contrast to the blue emission of the phase containing a DCM molecule and greenish-yellow emission of the acetone solvate in a crystal cell at room temperature. The potentially important role of co-crystallized solvent molecules in the ligand-based emission of the complex obtained is supported by DFT calculations.

Solid state solvation effect and reduced amplified spontaneous emission threshold value of glass forming DCM derivative in PMMA films

Molecule crystallization is one of the limitations for obtaining high-gain organic laser systems. One of the examples is well known red laser dye 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM). The lowest threshold value of amplified spontaneous emission was achieved by doping 2wt% of DCM molecule in tris-(8-hydroxy quinoline) aluminum (Alq3) matrix. Further increase of the DCM dye concentration makes the system less efficient as its threshold value increases. It is due to large intermolecular interaction, which induces photoluminescence quenching. Compounds with reduced intermolecular interaction could be prospective in organic laser systems due to higher possible doping.In this work photoluminescence and amplified spontaneous emission properties of modified DCM molecule in poly(methyl methacrylate) (PMMA) matrix were investigated. Bulky trityloxyethyl groups were attached to the donor part of DCM. These groups increase intermolecular distance wherewith reduce photoluminescence quenching. More than one order of magnitude lower excitation threshold energy of the amplified spontaneous emission was achieved in doped polymer films with investigated compound in comparison to doped polymer with DCM. It means that the investigated compound is more perspective as a laser material compared to the previously studied. In addition, amplified spontaneous emission maximum could be tuned within 15nm by changing concentration from 0.1wt% to 10wt% DWK-1 in PMMA matrix due to solid state solvation effect.

Guest driven structural transformation studies of a luminescent metal–organic framework

A two-dimensional (2D) porous metal-organic framework (MOF) [{Zn2(L) 4(OTf) 4}.2(DCM).xG]n (1 ⊃ G) (OTf = trifluoro methane sulfonate, DCM = Dichloromethane, L (1, 4-bis (4-pyridyl)-2, 3-diaza-1, 3-butadiene) synthesized at room temperature. Free guests DCM were encapsulated in the pores of the MOF. On air drying the MOF loses free DCM molecules and changed its structure in a crystal to crystal manner to produce compound 1 [{Zn(L)2(OTf)2}.XG]n(1). This guest-induced breathing of the framework was also supported from PXRD patterns. Solid state photoluminescence properties of the dynamic MOF were studied at room temperature. A 2D porous luminescent framework has been synthesized based on a long flexible N-donor ligand. The compound showed guest driven breathing of the framework. The guest dependent dynamic structural behaviour has been shown by SCSC experiments and PXRD patterns of the compound. Solid state UV and photoluminescence spectra were recorded for the compound at room temperature. Such structurally dynamic behaviour in conjunction with luminescence property of a metal organic framework might be very useful as a guest-responsive material for efficient separation purpose.

Tunable Two-color Luminescence and Host–guest Energy Transfer of Fluorescent Chromophores Encapsulated in Metal-Organic Frameworks

Co-assembly of chromophore guests with host matrices can afford materials which have photofunctionalities different from those of individual components. Compared with clay and zeolite materials, the use of metal–organic frameworks (MOFs) as a host structure for fabricating luminescent host–guest materials is still at an early stage. Herein, we report the incorporation of a laser dye, 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), into stilbene-based and naphthalene-based MOF systems. The resulting materials exhibit blue/red two-color emission, and the intensity ratio of blue to red fluorescence varies in different planes within the MOF crystal as detected by 3D confocal fluorescence microscopy. The observed changes in ratiometric fluorescence suggest the occurrence of energy transfer from MOF host to DCM molecules, which can be further confirmed by periodic density functional theoretical (DFT) calculations. Moreover, selective changes in luminescence behavior are observed on treating the guest@MOF samples with volatile organic compounds (methanol, acetone and toluene), indicating that these host–guest systems have potential applications as fluorescence sensors. It can be expected that by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels, a wide variety of multi-color luminescent and energy-transfer systems can readily be prepared in a similar manner.

Two-Photon Absorption of the DCM Molecule under Femtosecond Excitation between 720 and 920 nm

Nonlinear absorption of the DCM dye has been investigated by the two-quantum etalon method and the z-scan method with excitation by a tunable femtosecond Ti-sapphire laser (3 W, 140 fs, and 80 MHz). The two-photon absorption (TPA) spectrum of the DCM molecule has been obtained here for the first time between 720 and 920 nm and has been related to the absorption bands under linear excitation. It has been shown that in measurements of nonlinear absorption by the z-scan method the main contribution to changes in the transmittance comes from the triplet − triplet absorption.

Twenty-Fold Enhancement of Molecular Fluorescence by Coupling to a J-Aggregate Critically Coupled Resonator

We report a 20-fold enhancement in the fluorescence of the organic dye DCM when resonantly coupled to a strongly optically absorbing structure of a thin film of spin-deposited molecular J-aggregates in a critically coupled resonator (JCCR) geometry. A submonolayer equivalent of DCM molecules is shown to absorb and re-emit 2.2% of the incident resonant photons when coupled to the JCCR enhancement structure, compared to 0.1% for the bare film of same thickness on quartz. Such a JCCR structure is a general energy focusing platform that localizes over 90% of incident light energy within a 15 nm thin film layer in the form of excitons that can subsequently be transferred to colocated lumophores. Applications of the exciton-mediated concentration of optical energy are discussed in the context of solid-state lighting, photodetection, and single photon optics.

Orange−Blue−Orange Triblock One-Dimensional Heterostructures of Organic Microrods for White-Light Emission

1D triblock hetrostructures with striping patterns have been synthesized by doping 1,3-diphenyl-2-pyroline (DP) microrods with 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) molecules selectively at both ends. The middle stripe of triblock microds emit the blue light, while both ends emit orange light due to the efficient FET from excited DP to DCM molecules (right inset). Although triblock microrods show microarea heterogeneity in the striping pattern, they generate macroscopic high-quality white-light emission (WLE) in both the colloidal suspension (left inset) and the solid state with a photoluminescence efficiency as high as 36 +/- 5%.

Molecular Host−Guest Energy-Transfer System with an Ultralow Amplified Spontaneous Emission Threshold Employing an Ambipolar Semiconducting Host Matrix

We report on the characteristics of a host-guest lasing system obtained by coevaporation of an oligo(9,9-diarylfluorene) derivative named T3 with the red-emitter 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran dye (DCM). We demonstrate that the ambipolar semiconductor T3 can be implemented as an active matrix in the realization of a host-guest system in which an efficient energy transfer takes place from the T3 matrix to the lasing DCM molecules. We performed a detailed spectroscopic study on the system by systematically varying the DCM concentration in the T3 matrix. Measurements of steady-state photoluminescence (PL), PL quantum yield (PLQY), time-resolved picosecond PL, and amplified spontaneous emission (ASE) threshold are used to optimize the acceptor concentration at which the ASE from DCM molecules takes place with the lowest threshold. The sample with a DCM relative deposition ratio of 2% shows an ASE threshold as low as 0.6 kW/cm(2) and a net optical gain measured by femtosecond time-resolved pump-and-probe spectroscopy as high as 77 cm(-1). The reference model system Alq(3):DCM sample measured in exactly the same experimental conditions presents an one-order-of-magnitude higher ASE threshold. The ASE threshold of T3:DCM is the lowest reported to date for a molecular host-guest energy-transfer system, which makes the investigated blend an appealing system for use as an active layer in lasing devices. In particular, the ambipolar charge transport properties of the T3 matrix and its field-effect characteristics make the host-guest system presented here an ideal candidate for the realization of electrically pumped organic lasers.

Triplet States of the Nonlinear Optical Chromophore DCM in Single Crystals of Potassium Hydrogen Phthalate and Their Relationship to Single-Molecule Dark States

Single-molecule dark states are often attributed to photoexcited triplets with scant evidence of the participation of paramagnetic molecules. The photodynamics of blinking single molecules of 4-dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran (DCM) in crystals of potassium hydrogen phthalate (KAP) were compared with the lifetimes of DCM triplet states, likewise in KAP, whose zero-field splitting (ZFS) tensors were fully characterized by time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy. Luminescent mixed crystals of KAP were grown from solutions containing 10(-4) -10(-9) M DCM, a model optically nonlinear chromophore. The luminescent dye was localized in the {111} crystalline growth sectors. The photoexcited triplets states of DCM in the heavily dyed (10(-4) M) crystals were analyzed by TR-EPR spectroscopy. The photoexcited singlet states of DCM in lightly dyed crystals (10(-9) M) were analyzed by single-molecule microscopy. Large blue shifts in the absorption and emission spectra of DCM in KAP were interpreted as a consequence of protonation at the dimethylamino nitrogen atom, an assignment supported by calculations of the zero-field splitting (ZFS) tensors of molecules in their triplet states. Experimental ZFS tensors with eigenvalues comparable to those of the computed tensors were determined from the angular dependence of the EPR spectra of DCMH(+) triplets within KAP single crystals with respect to the applied magnetic field. Data from individual growth sectors failed to show magnetically equivalent site occupancies, evidence of the kinetic ordering during growth. The intermittent fluorescence of individual chromophores was analyzed. The distributions of on(off) times were characterized by distributed rates fit to power laws. The lifetime of the triplet states was analyzed from the time decay of the EPR signals between 100 and 165 K. The data were well fit with a single time constant for the signal decay, a result wholly inconsistent with the blinking of single molecules with off times commonly of tens of seconds. Triplet decay was extrapolated to approximately 25 micros at room temperature. Therefore, the assumption that single-molecule dark states originate with triplet excited states is not sustainable for single DCM molecules in KAP.

Theoretical study of solvent effect on one- and two-photon absorption properties of starburst DCM derivatives

The equilibrium geometries, electronic structures, one-photon absorption (OPA) and two-photon absorption (TPA) properties of starburst 4-(dicyanomethylene)-2-methyl-6-[p-(dimethylamino)styryl]-4H-pyran (DCM) derivatives have been studied by using density functional theory (DFT) and Zerner's intermediate neglect of differential overlap (ZINDO) program. Results showed that increasing the number of branches in DCM molecules and introducing stronger electron withdrawing groups are efficient ways to enhance the TPA cross sections. For the two- and three-branched molecules of the DCM derivatives, the solvent effect on the OPA and TPA properties was also considered by adapting the self-consistent reaction field (SCRF) theory with the polarizable continuum model (PCM) to model the interaction with the solvent in ZINDO program. The calculated molecular structure, transition dipole moment and intramolecular charge transfer (ICT) in different solvents have been analyzed to approximate how the solvent affects the TPA cross section. Results indicated that the TPA cross section increases as the polarity of the solvents increases, and it reaches a maximum when the dielectric constant epsilon equals 20.7.

DFT-PCM STUDIES OF THE SOLVENT EFFECTS ON THE ABSORPTION PROPERTIES OF DCM

In this paper, we have performed the optimized structures of the red emitting material, 4-(dicyanomethylene)-2-methyl-6-[p-(dimethyl amino) styryl]-4H-pyran (DCM), with different polarity solvent environments by using the density functional theory (DFT) method, B3LYP/6-31G*. The time-dependent density functional theory (TD-DFT) and the polarizable continuum model (PCM) have been used to obtain the optical properties in the solvent environment. It has been observed that when the solvent polarity increases, the DCM molecule exhibits the red shift in the maximum absorption wavelength [Formula: see text] and enhances the oscillator strength (f). The solvent polarity also enhances the electron transfer ability from the electron-donating dimethylamine group (-N(CH3)2) to the electron-withdrawing =C(CN)2group. The S0→ S1transition of DCM is found to be π–π*. The maximum absorption wavelengths [Formula: see text] of different solvent environments are found to be consistent with the reported experimental results.

Förster energy transfer in cholesteric mixtures: a new type of phototunable fluorescent material

A new approach to the creation of cholesteric glass‐forming materials with photovariable fluorescent properties is suggested. This approach is based on Förster type energy transfer from a photochemically active donor to a highly fluorescent acceptor. For this purpose, a cholesteric mixture containing two fluorescent dopants based on anthracene (Dianthr) and stilbene (DCM) was prepared and studied. The absorbance peak of DCM molecules overlaps the emission peak of Dianthr. The possibility of using energy transfer in cholesteric mixtures containing a photoactive energy donor capable of photobleaching is demonstrated. It is shown that UV irradiation of planarly oriented films of the mixture leads to photodimerization of the Dianthr dopant. This photoreaction results in a significant decrease in the emission intensity of the DCM dopant. In all cases the emitted light is strongly circularly polarized, and the degree of polarization does not change during photoreaction. Such types of photo‐patternable glass‐forming cholesteric materials combining fluorescent properties, the possibility of energy transfer between two fluorescent dyes and a photoactivity of one fluorescent component, provide new opportunities for optical data recording and storage.

Optimal thickness of hole transport layer in doped OLEDs

Current-voltage (I–V) and electroluminescence (EL) characteristics of organic light-emitting devices with N,N’-Di-[(1-naphthalenyl)-N,N’-diphenyl]-(1,1’-biphenyl)-4,4’-diamine (NPB) of various thicknesses as the hole transport layer, and tris(8-hydroxyquinoline)aluminum (Alq3) selectively doped with 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) as the electron transport layer, have been investigated. A trapped charge induced band bend model is proposed to explain the I–V characteristics. It is suggested that space charge changes the injection barrier and therefore influences the electron injection process in addition to the carrier transport process. Enhanced external quantum efficiency of the devices due to the electron blocking effect of an inserted NPB layer is observed. The optimal thickness of the NPB layer is experimentally determined to be 12±3 nm in doped devices, a value different from that for undoped devices, which is attributed to the electron trap effect of DCM molecules. This is consistent with the result that the proportion of Alq3 luminescence in the total electroluminescence (EL) spectra increases with NPB thickness up to 12 nm under a fixed bias.