Color Polymorphism and Room Temperature Phosphorescence of 4-bromo-2,7-di-tert-butyl-9-methoxypyrene.

The title compound has two polymorphic crystal structures having strikingly different absorption and luminescence spectra that result from different packing motifs in the crystal lattice. The polymorph with brick wall-like packing of molecules is white and shows very weak violet fluorescence whereas the second polymorph, where molecules are arranged in columnar stacks, is bright yellow and displays intense green fluorescence with maximum at 487 nm (20530 cm-1). In the white polymorph, where the distance between neighboring chromophores is increased, absorption and fluorescence spectra are similar to those of monomer in solution, and intersystem crossing to triplet manifold is the dominant pathway of relaxation. In the yellow polymorph, molecules within the columnar stacks are rotated which mitigates the steric hindrance and leads to closer π-stacking of the pyrene cores. That increases the ππ overlap and strengthens intermolecular interactions decreasing energy of the excited states. This affects emission spectra and photophysical processes - fluorescence yield grows whereas triplet formation yield decreases when S1 is lowered below higher triplet states and conditions for effective vibronic spin-orbit coupling are not favorable. The effect is not observed for other similar pyrene derivatives, testifying the uniqueness of the phenomenon.

Strong Chiroptical Effects in the Absorption and Emission of Macrocycles Based on the 2,5-Diaminoterephthalate Minimal Fluorophore.

Chiral fluorescent macrocycles consisting of two to four units of dimethyl 2,5-diaminoterephthalate can be readily synthesized in a one-pot manner from inexpensive building blocks. Depending on the concentration, either a paracyclophane-like dimer with closely stacked benzene rings or a triangular trimer is the main product of the reaction. The macrocycles exhibit fluorescence in solution as well as in the solid state with maxima that are red-shifted with decreasing size of the macrocyclic ring and are observed at wavelengths from 590 (tetramer in solution) to 700 nm (dimer in the solid state). Chirality dictates the differential absorption and emission of circularly polarized light by these molecules. The ECD and CPL effects are particularly strong for the trimer, which is characterized by relatively large dissymmetry factors gabs =±2.8×10-3 at 531 nm and glum =±2.3×10-3 at 580 nm in n-hexane, being at the same time highly luminescent (Φfl =13.7 %). Despite the small chromophore, the circularly polarized brightness BCPL of 2.3 dm3 mol-1 cm-1 is comparable to values reported for other classes of established CPL emitters in the visible region, such as expanded helicenes or larger π-conjugated systems.

Magnifying the ESIPT process in tris(salicylideneanilines) via the steric effect - a pathway to the molecules with panchromatic fluorescence.

Four tris(salicylideneanilines) (TSANs) with gradually increased steric interactions between the keto-enamine moiety and neighbouring phenyl substituent are presented. The steric interactions are induced by placing two alkyl groups at the ortho position in the N-aryl substituent. The impact of the steric effect over the radiative channels of deactivation of the excited state was evaluated through spectroscopic measurements and theoretical calculations using ab initio techniques. Our results show that the emission occurring after excited state intramolecular proton transfer (ESIPT) is favoured by placing the bulky groups in the ortho position of the N-phenyl ring of the TSAN. However, our TSANs seem to offer the opportunity to obtain a pronounced emission band at higher energy, significantly increasing the coverage of the visible spectrum, resulting in the enhancement of the dual emissive properties of tris(salicylideneanilines). Thus, TSANs may be promising molecules capable of white-like emission for use in organic electronic devices such as white OLEDs.

Harnessing Proton-Coupled Electron Transfer for Hydrogenation of Aza-Arenes: Photochemistry of Quinoxaline Derivatives in Methanol.

Three quinoxaline derivatives are investigated both experimentally and theoretically to assess their ability for the methanol oxidation and harvesting of hydrogen. In inert solvents, the nonplanar compounds exhibit very weak fluorescence from the lowest excited singlet state, whereas the planar and rigid chromophore emits non-Kasha fluorescence from the S2(ππ*) state despite the proximity of the S1(nπ*) state. In methanol, hydrogen-bonded complexes with solvent molecules are formed, and in all chromophores, the lowest singlet state is populated after excitation of the S2(ππ*) state. The switch from non-Kasha emission of the planar compound in inert solvents to regular emission in methanol is related to reduced symmetry of the hydrogen-bonded complex with methanol which results in effective mixing of ππ* and nπ* states and fast internal conversion to the lowest excited singlet state. The S1(nπ*) state of the hydrogen-bonded complex has charge-transfer character, and for all compounds in methanol, hydrogen transfer to the chromophore is observed. The chromophores retain the transferred hydrogen atoms, serving both as photocatalysts and as hydrogen storage materials. Undesired dark side reactions that occur are also discussed.

Photochemical Hydrogen Storage with Hexaazatrinaphthylene.

When irradiated with violet light, hexaazatrinaphthylene (HATN) extracts a hydrogen atom from an alcohol forming a long-living hydrogenated species. The apparent kinetic isotope effect for fluorescence decay time in deuterated methanol (1.56) indicates that the lowest singlet excited state of the molecule is a precursor for intermolecular hydrogen transfer. The photochemical hydrogenation occurs in several alcohols (methanol, ethanol, isopropanol) but not in water. Hydrogenated HATN can be detected optically by an absorption band at 1.78 eV as well as with EPR (electron paramagnetic resonance) and NMR techniques. Mass spectrometry of photoproducts reveal di-hydrogenated HATN structures along with methoxylated and methylated HATN molecules which are generated through the reaction with methoxy radicals (remnants from alcohol splitting). Experimental findings are consistent with the theoretical results which predicted that for the excited state of the HATN-solvent molecular complex, there exists a barrierless hydrogen transfer from methanol but a small barrier for the similar oxidation of water.

Polarized, V-Shaped, and Conjoined Biscoumarins: From Lack of Dipole Moment Alignment to High Brightness.

Eleven conjoined coumarins possessing a chromeno[3,4-c]chromene-6,7-dione skeleton have been synthesized via the reaction of electron-rich phenols with esters of coumarin-3-carboxylic acids, catalyzed by either Lewis acids or 4-dimethylaminopyridine. Furthermore, Michael-type addition to angular benzo[f]coumarins is possible, leading to conjugated helical systems. Arrangement of the electron-donating amino groups at diverse positions on this heterocyclic skeleton makes it possible to obtain π-expanded coumarins with emission either sensitive to, or entirely independent of, solvent polarity with large Stokes shifts. Computational studies have provided a rationale for moderate solvatochromic effects unveiling the lack of collinearity of the dipole moments in the ground and excited states. Depending on the functional groups present, the obtained dyes are highly polarized with dipole moments of ∼14 D in the ground state and ∼20-25 D in the excited state. Strong emission in nonpolar solvents, in spite of the inclusion of a NO2 group, is rationalized by the fact that the intramolecular charge transfer introduced into these molecules is strong enough to suppress intersystem crossing yet weak enough to prevent the formation of dark twisted intramolecular charge transfer states. Photochemical transformation of the dye possessing a chromeno[3,4-c]pyridine-4,5-dione scaffold led to the formation of a spirocyclic benzo[g]coumarin.

Polarized Helical Coumarins: [1,5] Sigmatropic Rearrangement and Excited-State Intramolecular Proton Transfer.

The tandem process of phenol addition to a cyclic α,ß-unsaturated ester followed by intramolecular transesterification and [1,5] sigmatropic rearrangement affords a series of helical coumarins based upon a previously unknown 3-amino-7-hydroxybenzo[3,4]cyclohepta[1,2-c]chromen-6-one core. These novel polarized coumarins, possessing a ß-ketoester moiety, have been employed to synthesize more rigid and helical coumarin-pyrazolones, which display green fluorescence. The enhanced emission of coumarin-pyrazolones in polar solvents depends on the nature of the S1 state. The coumarin-pyrazolones are predicted to have two vertical states close in energy: a weakly absorbing S1 (1LE) followed by a bright S2 state (1CT). In polar solvents, the 1CT can be stabilized below the 1LE and may become the fluorescent state. Solvatochromism of the fluorescence spectra confirms this theoretical prediction. The presence of an N-H···O═C intramolecular hydrogen bond in these coumarin-pyrazolone hybrids facilitates excited-state intramolecular proton transfer (ESIPT). This process leads to a barrierless conical intersection with the ground electronic state and opens a radiationless deactivation channel effectively competing with fluorescence. Solvent stabilization of the CT state increases the barrier for ESIPT and decreases the efficiency of the nonradiative channel. This results in the observed correlation between solvatochromism and an increase of fluorescence intensity in polar solvents.

Spectra and nature of the electronic states of [1]Benzothieno[3,2-b][1]benzothiophene (BTBT): Single crystal and the aggregates.

Absorption, fluorescence, and phosphorescence spectra of single crystals of [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and BTBT dispersed in frozen n-nonane, n-hexadecane, and dichloromethane matrices were studied at 5 K. Observation of a new absorption band and related changes in the fluorescence to phosphorescence intensity ratio, when the concentration of BTBT in the matrix increased above 10-4M, indicated the presence of BTBT aggregates. Quantum-chemistry calculations performed for the simplest aggregate, isolated dimer, showed that its structure is similar to the "herringbone" element in the BTBT crystal unit cell and the lowest electronic excited singlet state of the dimer has the intermolecular charge-transfer character. A qualitatively different nature of this state in dimers and in crystals, when compared with the situation in BTBT monomer [locally excited (LE) state], is associated with a decrease in the intersystem crossing yield. The structured vibronic structure of phosphorescence spectra in the studied systems indicated LE character of the triplet states.

Highly Polarized Coumarin Derivatives Revisited: Solvent-Controlled Competition Between Proton-Coupled Electron Transfer and Twisted Intramolecular Charge Transfer.

Linking a polarized coumarin unit with an aromatic substituent via an amide bridge results in weak electronic coupling that affects the intramolecular electron-transfer (ET) process. As a result of this, interesting solvent-dependent photophysical properties can be observed. In polar solvents, electron transfer in coumarin derivatives of this type induces a mutual twist of the electron-donating and -accepting molecular units (TICT process) that facilitates radiationless decay processes (internal conversion). In the dyad with the strongest intramolecular hydrogen bond, the planar form is stabilized, such that twisting can only occur in highly polar solvents, whereas a fast proton-coupled electron-transfer (PCET process) occurs in nonpolar n-alkanes. The kPCET rate constant decreases linearly with the energy of the fluorescence maximum in different solvents. This observation can be explained in terms of competition between electron- and proton-transfer from a highly polarized (ca. 15 D) and fluorescent locally excited (1 LE) state to a much less polarized (ca. 4 D) charge-transfer (1 CT) state, a unique occurrence. Photophysical measurements performed for a family of related coumarin dyads, together with results of quantum-chemical computations, give insight into the mechanism of the ET process, which is followed by either a TICT or a PCET process. Our results reveal that dielectric solvation of the excited state slows down the PCET process, even in nonpolar solvents.

Aggregation controlled photoluminescence of hexaazatri-naphthylene (HATN) - an experimental and theoretical study.

Photophysics of hexaazatrinaphthylene (HATN) in solution and in the solid state is determined by the nπ* character of its lowest excited singlet state and by the ππ* character of the first triplet state. The relaxation of an electronically excited state is dominated by nonradiative relaxation channels and only very weak fluorescence is observed for HATN monomers in solution. In liquid solution, the fluorescence quantum yield is 3-7 × 10-4 and the triplet formation yield ranges from 0.21 to 0.41. In methanol, the photodegradation of the molecule is observed. This molecule with a large delocalised π-electron system easily aggregates forming dimers in solution and in some crystalline forms. The band shifts observed in crystals as well as excitonic splitting in dimers provide evidence for a strong interaction in π-π stacked aggregates. The mixing of electronic states in aggregates changes their character and affects photophysical properties. The obtained experimental data are in good agreement with theoretical calculations performed using the ADC(2) method.

The Interplay between Solvation and Stacking of Aromatic Rings Governs Bright and Dark Sites of Benzo[g]coumarins.

Coumarins are classic, strongly polarized fluorophores with multiple applications, and significant efforts have been put into modifying their emission characteristics and elucidating their photophysics. Expecting that π-expansion of these donor-acceptor chromophores could modify their ground- and excited-state characteristics, the authors performed combined, detailed photophysical and computational studies of linearly π-expanded coumarins, that is, 8-dialkylamino-3-carboxyalkyl-benzo[g]coumarins. The investigation led to the conclusion that emission is only possible thanks to the stabilizing effect of the solvent and that breaking of the lactone ring leads to the conical intersection with the ground state and induces the radiationless decay of the electronic excitation. Aiming at the fine-tuning the excited state properties through the construction of covalently linked dye assemblies, the authors designed and synthesized a new bis(benzo[g]coumarin), built from two similar moieties that exhibit different degrees of polarization due to the electron donor at position 8: one possesses a dialkylamino, and the other a weaker amide donor. Comprehensive studies have shown that the observed weak fluorescence of the system is the result of the interplay between the solvation-induced separation of the benzo[g]coumarin moieties, which stabilizes the emitting locally excited singlet state and the π-stacking interactions, favoring their sandwiched orientation and leading to the non-emissive charge-transfer state.

The synthesis and photophysical properties of tris-coumarins.

A structurally unique cyclic tris-coumarin possessing three identical coumarin units bridged by amide linkers as well as two linear analogs has been synthesized. There is a remarkable agreement between crystallographic data, 1H NMR and results of calculations for the cyclic tris-coumarin, showing in all cases a non-symmetric arrangement of identical coumarin moieties. Weak polarization of the coumarin subunits, resulting from the presence of only CONH- groups as electron-donors, results in a hypsochromic shift of both absorption and emission in this dye. We have proven that in non-cyclic, head-to-tail linked tris-coumarins, the photophysics is controlled not only by the substituents but also by the conformation of the molecule, which in turn depends on the nature of the linker's interactions. These can be controlled by the presence/absence of an amide-type hydrogen atom responsible for the formation of intramolecular hydrogen bonds. The presence of a hydrogen bond favors a stretched trans conformation of the dye, while in its absence, folding of the molecule occurs leading to a more compact conformation. Although, the increased number of covalently linked coumarin units does not drastically change the preferred conformation, the fluorescence quantum yields of tris-coumarins are significantly lower than for analogous bis-coumarins composed of the same units.

Effect of conformational flexibility on photophysics of bis-coumarins.

The fluorescence intensity of bis-coumarins linked via CONH and COO functionalities are shown to exhibit a strong dependance on solvent polarity. The presence of the intramolecular hydrogen bond between the C[double bond, length as m-dash]O oxygen atom of coumarin and amide-NH moieties reduces the number of thermodynamically populated conformations in both ground and electronically excited states and an anti-arrangement of coumarin units is favored. Additionally, the rigidity of the linker raises the barrier to the conical intersection with the ground state, and in non-polar solvents strong fluorescence is observed. Although changing the CONH linking position from 3-7' to 3-6', does not remarkably affect the photophysics, replacement with a flexible ester linker allows the molecule a greater degree of conformational freedom due to the absence of the intramolecular hydrogen bonding interaction. The photophysical effect of this is the appearance of two fluorescence bands, the relative intensity and spectral positions of which are sensitive to the environment. Theoretical explorations of the excited-state potential energy surfaces performed with the aid of the ADC(2) ab initio electronic structure theory method revealed an exceptional wealth of concomitant photophysical processes. In particular, two channels for radiationless deactivation of the excited state were found; the first is related to the inter-ring twist of the coumarin units, and the second is associated with the excited-state intramolecular proton-transfer (ESIPT) from the CONH linker to the coumarin core.

Fluorescence of 4-(Diisopropylamino)benzonitrile (DIABN) Single Crystals from 300 K down to 5 K. Intramolecular Charge Transfer Disappears below 60 K.

Single crystals of 4-(diisopropylamino)benzonitrile (DIABN) undergo an intramolecular charge transfer (ICT) reaction in the excited singlet state. At 300 K, the fluorescence consists of emissions from the locally excited (LE) and from the ICT state. Upon cooling to 5 K, the ICT fluorescence intensity gradually decreases relative to that of the LE emission and is absent below 60 K. With crystalline 4-(dimethylamino)benzonitrile (DMABN), in contrast, only LE emission is found over the entire range from 300 to 5 K. The phosphorescence spectra of the DIABN and the DMABN crystals do not present any evidence for an additional ICT emission, showing that ICT does not occur in the triplet state. An activation energy Ea of ∼4 kJ/mol is determined for the LE → ICT reaction of DIABN crystals, from the temperature dependence of the fluorescence decay times τ2 and τ1. Ea is attributed to changes in the molecular conformation of DIABN other than a full rotation of the large diisopropylamino group with respect to the benzonitrile moiety. In a comparison with crystal and solution data, literature results from transient vibrational and absorption spectra are discussed and it is concluded that they cannot be employed to favor the TICT (perpendicular twist) over the PICT (planar) model for DIABN and DMABN.

The Coumarin-Dimer Spring-The Struggle between Charge Transfer and Steric Interactions.

The synthesis of a weakly coupled, strongly polarized coumarin dimer has been achieved for the first time. The three-step strategy comprises the Skattebøl formylation followed by the Knoevenagel reaction and the formation of a tertiary amide by using a peptide-type procedure. The molecule consists of two different coumarin moieties: One is a classical donor-acceptor system and the second one possesses a weaker amide donor at the 7-position. The polarized coumarin dimer can form an electronically conjugated structure possessing an electric dipole larger than that of 7-(dimethylamino)coumarin-3-carboxylic acid. The limited flexibility of the inter-coumarin connection results in stable conformers of different electric dipole moments and complex photophysics. In the solid state, this compound has a strongly bent conformation with the two coumarin units forming an angle of around 74°. In solution, two conformers are in equilibrium. The existence of the molecule as two conformers in the ground state has been confirmed by optical studies, and further corroborated by molecular calculations. The fluorescence spectra possess a unique feature: A charge-transfer band (ca. 550 nm) is visible only in nonpolar or weakly polar solvents. Optical spectroscopy studies coupled with molecular calculations allowed us to rationalize this phenomenon: The large amplitude of intramolecular motions is responsible for the conformational isomerization as well as producing a conical intersection between the potential energy surfaces of the excited singlet state and the ground state, which opens an internal conversion channel that effectively competes with the fluorescence of the conformers.

Environment-Sensitive Behavior of DCNP in Solvents with Different Viscosity, Polarity and Proticity.

A pyrazoline derivative, 3-(1,1-dicyanoethenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DCNP), is studied by using optical spectroscopy methods in several solvents at room and at low temperatures. The DCNP molecule reveals a complex photophysics behavior, which is sensitive to solvent polarity, proticity, temperature and viscosity and arises from the presence of two rotational degrees of freedom of the dicyanovinyl group--the torsion around the double C=C bond and the s-trans-s-cis isomerization around the single C-C bond--that differently behave in various environmental conditions. The fluorescence yield of a few percent and sub-nanosecond decay times observed at room temperature make the compound useful for optical studies of liquid environments. The proticity of polar solvents can be detected with two-exponential fluorescence decays. At low temperatures, DCNP can be used as solvent viscosity or temperature fluorescent sensor.

Carbonyl mediated fluorescence in aceno[n]helicenones and fluoreno[n]helicenes.

Helicenes are very attractive chiral non-planar polycyclic aromatic hydrocarbons possessing strong chiroptical properties. However, most of the helicenes absorb light mainly in the ultraviolet region, with only a small segment in the blue part of the visible spectrum. Furthermore, carbo[n]helicenes exhibit only weak luminescence that limits their utilization. Herein, we demonstrate that peripheral decoration of the helicene backbone with an aryl-carbonyl group shifts the absorption to the visible region and simultaneously improves their fluorescence quantum yields. We thus show that the carbonyl group, commonly considered as detrimental to emission, has the capability of improving optical and photophysical properties. Two different families, aceno[n]helicenones and fluoreno[n]helicenes, are presented with comprehensive spectrochemical characterization. TD-DFT calculations were implemented to clarify their electronic profiles. We show that increasing the helical length in aceno[n]helicenes increases absorption onset, g abs and g lum. Extension of the peripheral aromatic part in fluoreno[n]helicenes leads to a blue shift in both absorption and emission.

Fluorene analogues of xanthenes - low molecular weight near-infrared dyes.

Fluorene-based analogues of fluorescein, rhodol, and rhodamine exhibit absorption and fluorescence beyond 800-900 nm in water, 300-400 nm red-shifted compared to the original oxygen-bridged xanthene dyes, giving potential access to low molecular weight fluorescent markers for the second biological window (NIR-II, ca. 1000-1350 nm).