Ion-Pairing Assemblies of Anion-Responsive π-Electronic Systems That Have Noncovalently Assisted Expanded Planar Region.

Arylethynyl-substituted dipyrrolyldiketone BF2 complexes as anion-responsive π-electronic molecules exhibited characteristic electronic properties derived from conformation changes upon anion binding, which caused an increase in UV/vis absorption and associated two-photon absorption.  The anion complexes showed expanded planar regions assisted by intramolecular interactions, resulting in charge-by-charge ion-pairing assemblies in the solid state.

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene derivative.

Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene (fDAE) derivative were investigated by time-resolved absorption and fluorescence spectroscopies. Prescreening with quantum chemical calculation predicted that a derivative with methylthienyl groups (mt-fDAE) in the closed-ring isomer has a two-photon absorption cross-section larger than 1000 GM, which was experimentally verified by Z-scan measurements and excitation power dependence in transient absorption. Comparison of transient absorption spectra under one-photon and simultaneous two-photon excitation conditions revealed that the closed-ring isomer of mt-fDAE populated into higher excited states deactivates following three pathways on a timescale of ca. 200 fs: (i) the cycloreversion reaction more efficient than that by the one-photon process, (ii) internal conversion into the S1 state, and (iii) relaxation into a lower state (S1' state) different from the S1 state. Time-resolved fluorescence measurements demonstrated that this S1' state is relaxed to the S1 state with the large emission probability. These findings obtained in the present work contribute to extension of the ON-OFF switching capability of fDAE to the biological window and application to super-resolution fluorescence imaging in a two-photon manner.

Photocatalytic CO2 Reduction Using an Osmium Complex as a Panchromatic Self-Photosensitized Catalyst: Utilization of Blue, Green, and Red Light.

The photocatalytic reduction of carbon dioxide (CO2) represents an attractive approach for solar-energy storage and leads to the production of renewable fuels and valuable chemicals. Although some osmium (Os) photosensitizers absorb long wavelengths in the visible-light region, a self-photosensitized, mononuclear Os catalyst for red-light-driven CO2 reduction has not yet been exploited. Here, we discovered that the introduction of an Os metal to a PNNP-type tetradentate ligand resulted in the absorption of light with longer-wavelength (350-700 nm) and that can be applied to a panchromatic self-photosensitized catalyst for CO2 reduction to give mainly carbon monoxide (CO) with a total turnover number (TON) of 625 under photoirradiation (λ≥400 nm). CO2 photoreduction also proceeded under irradiation with blue (λ0=405 nm), green (λ0=525 nm), or red (λ0=630 nm) light to give CO with >90 % selectivity. The quantum efficiency using red light was determined to be 12 % for the generation of CO. A catalytic mechanism is proposed based on the detection of intermediates using various spectroscopic techniques, including transient absorption, electron paramagnetic resonance, and UV/Vis spectroscopy.

Phosphorus(V) Tetraazaporphyrin with an Intense, Broad CT Band in the Near-IR Region.

In phosphorus tetraazaporphyrins (PTAPs), the Q- and charge-transfer (CT) bands appear as a result of configuration interaction between their excited states. On the basis of this concept, a PTAP with an intense, broad CT band in the near-IR region has been rationally designed and realized by introducing eight diphenylaminophenyl (dPAP) groups. The order of the CT and Q-bands in ascending energy was supported by magnetic circular dichroism (MCD) spectroscopy and theoretical calculations. An intense two-photon absorption was also found in the deep near-IR region.

Two-photon absorption properties of simple neutral Ir(III) complexes.

A series of neutral Ir(2-phenylpyridine)3 derivatives substituted on the para-position of the pyridyl ligands with a π-conjugated substituent possessing different donor abilities has been prepared. Their two-photon absorption properties have been determined using the Z-scan technique. Such simple iridium(III) neutral complexes, which are easy to synthesize, show good two-photon absorption activity, with relevant TPA cross sections (the best is 750 GM), giving rise to multifunctional chromophores, since they present also high second-order NLO properties.

Enhanced near infrared-to-visible upconversion in the CaTiO3:Yb3+/Er3+ phosphor via the host lattice modification using co-doping of Mg2+ ions.

The CaTiO3:Er3+/Yb3+ upconversion phosphor was synthesized using a simplified co-precipitation method and the effect of Mg2+ ion co-doping was investigated on the structural and optical properties focusing on the near-infrared (NIR)-to-visible upconversion. The introduction of Mg2+ ions into the host lattice produced substantial changes in the crystal structure, grain size, and absorption, thus leading to the enhancement in upconversion emission intensities. X-ray diffraction (XRD) analysis indicated the formation of polycrystalline CaTiO3-Ca4Ti3O10 composite crystals and an increase in the crystallite size was observed upon increasing the Mg2+ ion concentration in the samples. Elemental analysis by energy dispersive spectroscopy (EDS) suggested the substitution of Ca2+ ions by Mg2+ ions in the CaTiO3 host lattice. Moreover, a change in the Yb3+/Er3+ ratio from 0.25 to 1.1 indicated the redistribution of the Er3+ or Yb3+ ions caused by the Mg2+ ions. These lattice deformations further resulted in an improved absorption of Er3+ ions, exhibiting a ∼3-fold enhancement in the upconversion emission intensity (at the excitation intensity of ∼1 W cm-2).

Intramolecular Singlet Fission in Pentacene Oligomers via an Intermediate State.

Intramolecular singlet fission (iSF) is an efficient strategy of multiexciton generation via a singlet exciton splitting into a correlated triplet pair in one organic molecule with more than two chromophores. Propeller-shaped iptycene-linked triisopropylsilyl(TIPS)-ethynyl functionalized pentacene oligomers (pent-monomer, pent-dimer, and pent-trimer) were synthesized, and the iSF dynamics of pent-dimer and -trimer were monitored by a visible-near-IR transient absorption (TA) spectroscopy. Quantum yields of the triplet pair, ∼80%, of both estimated by near-IR TA spectral analysis are in good agreement with the results of global analysis and triplet sensitization experiments. The iSF rate of pent-trimer is slightly faster than that of pent-dimer even with one more chromophore site. The unexpectedly weak difference indicates the existence of an intermediate process to realize iSF. The intermediate process might be determined by through-bond electronic coupling of the homoconjugation bridge in the pentacene oligomers. Our results suggest the importance of the rigid bridge to the fast iSF rate and the elongated lifetime of the correlated triplet pair in pentacene oligomers.

Unveiling a new aspect of oxocarbons: open-shell character of 4- and 5-membered oxocarbon derivatives showing near-infrared absorption.

Oxocarbon derivatives consisting of 4- and 5-membered rings, referred to as croconaine and squaraine dyes and regarded as closed-shell molecules, are found to have an intermediate open-shell character from the experimental results of 1H-NMR, ESR spectroscopy, SQUID magnetometric analysis, and X-ray crystallography. We employed two chalcogenopyrylium moieties with O and S chalcogen atoms as substitutions on oxocarbons. The singlet-triplet energy gaps (ΔE S-T) associated with the degree of diradical nature are smaller for croconaines than for squaraines and smaller for thiopyrylium than for pyrylium groups. The diradical nature impacts the electronic transition energy that decreased with a decreasing degree of diradical contribution. They exhibit substantial two-photon absorption in the region over 1000 nm. The diradical character y of the dye was determined experimentally from the observed one- and two-photon absorption peaks and the triplet energy level. The present finding provides new insight into diradicaloids with the contribution of non-Kekulé oxocarbon and also showcases the correlation between the electronic transition energy and their diradical character.

Importance of steric bulkiness of iridium photocatalysts with PNNP tetradentate ligands for CO2 reduction.

A series of Ir complexes has been developed as multifunctional photocatalysts for CO2 reduction to give HCO2H selectively. The catalytic activities and photophysical properties vary widely across the series, and the bulky group insertion resulted in the formation of HCO2H and CO with the catalyst turnover number of >10 400.

Oxidative Cyclodehydrogenation of Trinaphthylamine: Selective Formation of a Nitrogen-Centered Polycyclic π-System Comprising 5- and 7-Membered Rings.

We describe a new type of nitrogen-centered polycyclic scaffold comprising a unique combination of 5-, 6-, and 7-membered rings. The compound is accessible through an intramolecular oxidative cyclodehydrogenation of tri(1-naphthyl)amine. To the best of our knowledge this is the very first example of a direct 3-fold cyclization of a triarylamine under oxidative conditions. The unusual ring fusion motif is confirmed by X-ray crystallography and the impact of cyclization on the electronic and photophysical properties is investigated both experimentally and theoretically based on density-functional theory (DFT) calculations. The formation of the unexpected product is rationalized by detailed mechanistic studies on the DFT level. The results suggest the cyclization to occur under kinetic control via a dicationic mechanism.

Triplet-triplet annihilation photon upconversion from diphenylhexatriene and ring-substituted derivatives in solution.

We report that diphenylhexatriene (DPH) and its ring-substituted derivatives act as emitter molecules in triplet-triplet annihilation photon upconversion (TTA-UC). A palladium porphyrin derivative, meso-tetraphenyl-tetrabenzoporphine palladium complex (PdTPBP), which acts as a sensitiser in TTA-UC, and DPH derivatives were dissolved in tetrahydrofuran (THF). The solution showed blue-green to green UC emission under photoexcitation at 640 nm in a nitrogen atmosphere. The UC quantum efficiency (ηUC) values of the DPHs were estimated, with (E,E,E)-1,6-bis[4-(di-2-picolylamino)phenyl]hexa-1,3,5-triene (pico DPH) showing the highest. In addition, the quantum yields of triplet energy transfer (TET) and triplet-triplet annihilation (TTA), which are elementary processes in TTA-UC, were estimated, as well as the triplet lifetimes of each DPH derivative. The results indicate that the TTA process governs the value of ηUC.

From 2,5-Diformyl-1,4-dihydropyrrolo[3,2-b]pyrroles to Quadrupolar, Centrosymmetric Two-Photon-Absorbing A-D-A Dyes.

An original approach has been developed for the insertion of formyl substituents at positions 2 and 5 of 1,4-dihydropyrrolo[3,2-b]pyrroles by conversion of thiazol-2-yl substituents. The synthetic utility of these formyl groups was investigated, and a series of centrosymmetric A-π-D-π-A frameworks were constructed. The two-photon absorption of the quadrupolar pyrrolo[3,2-b]pyrrole possessing two dicyanovinylidene flanking groups is attributed to an S0 → (S1) → S4 transition which has a large TPA cross-section (1300 GM) for a molecule of this size.

Kinetics of photon upconversion by triplet-triplet annihilation: a comprehensive tutorial.

This perspective article provides a comprehensive but organized tutorial introduction of the kinetics related to photon upconversion (UC) by triplet-triplet annihilation (TTA) (TTA-UC). The field of TTA-UC is multi-disciplinary and rapidly growing with the involvement of researchers from diverse backgrounds. TTA-UC consists of a series of tangled photophysical processes, so a solid understanding of the kinetic features and consequences is important to develop and evaluate materials for TTA-UC. This tutorial starts with an introduction of the standard model of TTA-UC along with the assumptions used in the model. The essential concept of the spin statistics for TTA and how this concept is related to the singlet branching ratio, which directly affects the efficiency of UC, are then explained through step-by-step analyses. Using these foundations, solutions for the steady-state behaviors are derived, featuring the universal curve that describes the excitation intensity dependence of the UC quantum yield for any sample type. Various useful functions for analyzing experimental data are also introduced and summarized. The transient behaviors of TTA-UC are then discussed along with their equations, and the usefulness for analyzing transient experimental data is explained using examples. In this article, self-consistent derivations and relevant references are provided for an easy understanding of the advanced discussion and analyses.

Molecular crystalline capsules that release their contents by light.

Here, we present single crystalline capsules of a photoresponsive molecule produced by simple recrystallization from organic solutions without direct human processing. During the crystal growth process, a movie was taken of the capsule taking in the organic solution. The capsules responded rapidly (<1 s) to the UV light stimuli and released the captured solution or solute. In principle, they can take in any substance dissolved in organic solvents, and their size can be controlled. Moreover, the capsule can be broken by multi-photon excitation using a near-infrared laser within the biological window. Furthermore, because the molecular packing in the crystal is unidirectional, the response can be controlled by the polarization of the light. This study shows the new potential of photoresponsive molecules.

Quadrupolar Dyes Based on Highly Polarized Coumarins.

The fluorescence and other photophysical parameters of highly polarized, quadrupolar bis-coumarins possessing an electron-rich pyrrolo[3,2-b]pyrrole bridging unit are highly dependent on the linking position between both chromophores. Delocalization of the LUMO on the entire π-system results in intense emission and strong two-photon absorption.

Anion-Responsive Molecules That Exhibit Switching of Two-Photon Optical Properties.

Two-photon-excited fluorescent probes are important for two-photon microscopy for biomedical studies. In contrast to the many examples of probes for cationic species, such as metal ions, there have been fewer reports on the control of two-photon optical properties by anions because in such systems it is difficult to control the associated π-electronic states. This Minireview summarizes anion-responsive molecules that exhibit changes in two-photon optical properties and describes their molecular design and anion-response mechanisms, which are driven by changes in covalent bonds and noncovalent interactions. Results from a recent study of two-photon systems, where geometries and optical properties are modulated by anion binding, are also discussed.

Triplet-triplet annihilation upconversion through triplet energy transfer at a nanoporous solid-liquid interface.

We report the triplet-triplet annihilation (TTA) upconversion (UC) through triplet energy transfer (TET) from a sensitiser fixed on a solid surface to free emitters dissolved in solution. A carboxylic-acid derivative of Pt-porphyrin was used as the sensitiser fixed on an amino-treated surface of continuous nanoporous glass without aggregation. UC emission was observed under photoexcitation of 532 nm for porphyrin-fixed glass immersed in an emitter solution of 9,10-diphenylanthracene (DPA), showing that TET occurs through the solid-liquid interface. The dynamics of TET was analysed through both phosphorescence decay of the sensitiser and UC emission rise from the emitter. Two TET components with different rate constants were found, slower than diffusion-controlled reactions in solution by 1-2 orders of magnitude. Nevertheless, the solid surface TET rates were fast enough to obtain a high quantum yield over the solid-liquid interface. By melting DPA and soaking it into sensitiser-fixed porous glass, we fabricated an all-solid system enabling TTA-UC through the bulk interface.

Photocatalytic CO2 Reduction Using a Robust Multifunctional Iridium Complex toward the Selective Formation of Formic Acid.

A highly efficient tetradentate PNNP-type Ir photocatalyst, Mes-IrPCY2, was developed for the reduction of carbon dioxide. The photocatalyst furnished formic acid (HCO2H) with 87% selectivity together with carbon monoxide to achieve a turnover number of 2560, which is the highest among CO2 reduction photocatalysts without an additional photosensitizer. Mes-IrPCY2 exhibited outstanding photocatalytic CO2 reduction activity in the presence of the sacrificial electron source 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) in CO2-saturated N,N-dimethylacetamide under irradiation with visible light. The quantum yield was determined to be 49% for the generation of HCO2H and CO. Electron paramagnetic resonance and UV-vis spectroscopy studies of Mes-IrPCY2 with a sacrificial electron donor revealed that the one-electron-reduced species is the key intermediate for the selective formation of HCO2H.

Switching of Two-Photon Optical Properties by Anion Binding of Pyrrole-Based Boron Diketonates through Conformation Change.

Two-photon absorption (TPA) dyes with intense fluorescence can be used to detect small chemical species and as sensors and bioimaging probes for specific analytes. Various TPA dyes responding to a number of external stimuli have been reported. Among them, biologically important anionic species have not been used as agents to control TPA properties because their direct electronic influences on the transition dipole moments of dyes are typically small. In this study, dipyrrolyldiketone BF2 complexes substituted with π-extended units exhibited efficient TPA properties that could be regulated by conformation changes induced by anion binding. The TPA intensity decreased to 1/5 of the original intensity upon anion binding, which was much larger than that observed for one-photon absorption. Anion detection was achieved by a change in the emission intensity of spatially resolved spots of two-photon-excited fluorescence (TPEF) in the sample. Experimental and theoretical studies were performed to understand the mechanism of the TPA property control and showed that the drastic changes in the transition dipole moments upon conformation changes between the straight and bending forms of the π-electronic systems caused the TPA and TPEF intensities drop.

Chalcone-based molecules: Experimental and theoretical studies on the two-photon absorption and molecular first hyperpolarizability.

Five chalcone-based molecules denominated by C-3 ((E)-1-(4-methoxyphenyl)-3-phenylprop-2-en-1-one), C-4 ((E)-1,3-bis(4-methoxyphenyl)prop-2-en-1-one), C-5 ((E)-1-(benzo[d][1,3]dioxol-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one), C-6 ((E)-3-(naphthalen-1-yl)-1-phenylprop-2-en-1-one) and C-7 ((E)-1-(4-methoxyphenyl)-3-(naphthalen-1-yl)prop-2-en-1-one) were synthesized by Claisen-Schmidt reaction in solution of NaOH in water/ethanol 2:1. The aldehydes used were benzaldehyde, anisaldehyde, and ß-naphthaldehyde, while the used ketones were acetophenone, p-methoxyacetophenone, and 3,4-methylenedioxyacetophenone. Z-scan and hyper-Rayleigh scattering techniques were used to study the nonlinear optical properties of these compounds in dichloromethane medium. By using Z-scan technique with femtosecond pulses, two-photon absorption cross-sections (σTPA) were determined, while the first molecular electronic hyperpolarizabilities (ßHRS) were evaluated by the hyper-Rayleigh scattering technique, with picosecond pulses. From the recorded two-photon absorption spectra, it was identified that compound C-7 presented the highest σTPA, regarding the HOMO-LUMO transition, with a value of 40 GM, while C-6 achieved the lowest value for the same transition with 13 GM. Concerning the values of the first molecular hyperpolarizability, compound C-4 presented the highest value, 38 × 10-30 cm4 statvolt-1, while C-3 presented the lowest ßHRS value of about 16 × 10-30 cm4 statvolt-1. Time-dependent density functional theory calculations were used to simulate the one- and two-photon absorption spectra, as well to predict the theoretical value of ßHRS in dichloromethane and vacuum medium.