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Daniele Marinotto

Daniele Marinotto
The National Research Council (Cnr) · Istituto di Scienze e Tecnologie Chimiche (SCITEC) "Giulio Natta"

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62
Publications
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1,768
Citations
Citations since 2017
32 Research Items
1343 Citations
2017201820192020202120222023050100150200250
2017201820192020202120222023050100150200250
2017201820192020202120222023050100150200250
2017201820192020202120222023050100150200250
Introduction
Daniele Marinotto currently works at the Institute of Chemical Sciences and Technologies (SCITEC) "Giulio Natta" - CNR Research Centres. Daniele does research in Materials Chemistry, Polymer Chemistry and Nanotechnology. Their most recent publication is 'Cyclic Triimidazole Derivatives: Intriguing Cases of Multiple Emissions and RT Ultralong Phosphorescence'.

Publications

Publications (62)
Article
Full-text available
The coordination ability of the pyridine derivative of cyclic triimidazole, namely 3-(pyridin-2-yl)triimidazotriazine (TT-Py) towards Cu(I) was explored. TT-Py is an appealing nitrogen-rich ligand characterized by the presence of three imidazole nitrogen atoms with trigonal symmetry and a pyridine moiety, available for coordination to metal ions. T...
Article
Full-text available
The development of organic room-temperature phosphorescent (ORTP) materials represents an active field of research due to their significant advantages with respect to their organometallic counterparts. Two cyclic triimidazole (TT) derivatives bearing one and three hexyl-thiophene moieties, TT-HThio and TT-(HThio)3, have been prepared and characteri...
Article
Three novel luminescent iridium(III) dyes functionalized with a tryptophan amino acid and bearing two cyclometalated 2-phenylpyridines, 2-(2,4-difluorophenyl)pyridines or 2-phenylquinolines have been prepared and well characterized. They emit at 522–561 nm with a luminescence quantum yield in the range 0.33–0.98. All the dyes are able to stain neur...
Article
Substitution of the chlorido ligand of cyclometalated [Pt (5-R-1,3-di(2-pyridyl) benzene)Cl] (R = methyl, mesityl, 2-thienyl, or 4-diphenylamino-phenyl) by 4-phenylthiazole-2-thiolate leads to related thiolato complexes, which were fully characterized. Their photophysical properties were determined in degassed dichloromethane solution. The emission...
Article
Two derivatives of cyclic triimidazole and pyrene, namely the blue emitting 3-(pyren-1-yl)triimidazo[1,2-a:1′,2′-c:1″,2″-e] [1,3,5]triazine, TTPyr, and the yellow-orange emitting 11-(pyren-1-yl)triimidazo[1,2-a:1′,2′-c:1″,2″-e] [1,3,5]triazine-3,7-dicarbaldehyde, (CHO)2TTPyr, are here exploited for titration experiments with various nitroaromatic e...
Article
The preparation and characterization of three new complexes, namely [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-4,6-difluoro-benzene)Cl] ([PtL1Cl]), [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-5-triphenylamine-benzene)Cl] ([PtL2Cl]), and [Pt(1,3-bis(4-triphenylamine-pyridin-2-yl)-5-mesityl-benzene)Cl] ([PtL3Cl]), is reported. All of them are highly l...
Article
Full-text available
A QTAIM and IQA investigation on model compounds of two isostructural Ag I and Cu I coordination polymers (CPs) based on cyclic triimidazole ( L ), i.e. the [ M I L ] n 1D double-stranded stair chain and the [ M Cl L ] n 3D network ( M = Cu, Ag), has allowed light to be shed on the different emissive behaviour associated with the two metal ions. Ac...
Article
Substitution of the chlorido ligand of the fascinating cyclometalated complex [Pt(5-mesityl-1,3-di(2-pyridyl)benzene)Cl] by thioacetate leads to the related thiolato complex [Pt(5-mesityl-1,3-di(2-pyridyl)benzene)(thioacetate)], which has been fully characterised. Its photophysical properties were determined in degassed dichloromethane solution, as...
Article
Full-text available
The search of new organic emitters is receiving a strong motivation by the development of ORTP materials. In the present study we report on the preparation, optical and photophysical characterization, by both steady state and time resolved techniques, of two pyrene-functionalized cyclic triimidazole derivatives. Together with the already reported m...
Article
Full-text available
Organic materials with multiple emissions tunable by external stimuli represent a great challenge. TTPyr, crystallizing in different polymorphs, shows a very rich photophyisics comprising excitation‐dependent fluorescence and phosphorescence at ambient conditions, and mechanochromic and thermochromic behavior. Transformation among the different spe...
Article
Full-text available
Purely organic luminophores that exhibit room temperature phosphorescence (RTP) are receiving an ever growing attention. The design of efficient RTP materials and the understanding of their emissive behaviour, however, remain a challenging task. Herein, to gain further insights into metal‐free RTP, we report the synthesis, characterization and phot...
Article
The possibility to control luminescent properties of purely organic emitting salts is receiving an ever-growing interest. A full understanding of the manifold effects of counterions on the photophysics of charged...
Article
The remarkable emissive properties of cyclic triimidazole (TT), showing crystallization-induced emissive behavior and, in particular, room temperature phosphorescence (RTP), are here combined with its versatility in assembling coordination compounds. A series of Ag(I) coordination polymers (CPs), comprising a 1D chain ([Ag(TT)I]n, 1-Ag) and 3D netw...
Article
Full-text available
The development of purely organic materials showing multicolor fluorescent and phosphorescent behaviour represents a formidable challenge in view of practical applications. Herein the rich photophyisical behaviour of 3-(pyridin-2-yl)triimidazotriazine (TT-Py) organic molecule, comprising excitation-dependent fluorescence and phosphorescence under a...
Article
Full-text available
The second-order nonlinear optical (NLO) properties of iridium(III) complexes having two cyclometalated 2-phenylpyridines and curcumin or tetrahydrocurcumin as ancillary ligand have been investigated both in solution and as guest in a polymeric organic matrix. In solution, these complexes are characterized by a significant second-order NLO response...
Article
The preparation and characterization of a new platinum(II) complex bearing a N^C^N-cyclometalating ligand and a thiolate coligand, namely 5-mesityl-1,3-di-(2-pyridyl)benzene and 1-phenyl-1H-tetrazole-5-thiolate, is reported. Its structure is determined by X-ray diffraction studies on a single crystal. This new complex exhibits green and red phospho...
Article
Full-text available
Whereas there is an increasing amount of reports on the second-order nonlinear optical (NLO) and luminescence properties of tetradentate [N2O2] Schiff base–zinc complexes, the study of zinc complexes having two bidentate [NO] Schiff-base ligands is relatively unexplored from an NLO point of view. This work puts in evidence that the known chiral bis...
Article
New Y-shaped ferrocene conjugated imidazole chromophores were prepared and fully characterized. The Y-shaped structure was confirmed by the single crystal X-ray diffraction technique. The chromophores show interesting second-order nonlinear optical (NLO) properties in solution, as determined by the Electric-Field Induced Second Harmonic generation...
Article
Full-text available
Organic room temperature persistent luminescence is a fascinating but still largely unexplored phenomenon. Cyclic-triimidazole and its halogenated (Br, I) derivatives have recently revealed as intriguing phosphors characterized by multifaceted emissive behavior including room temperature ultralong phosphorescence (RTUP) associated with the presence...
Article
Structures and properties, including second-order non-linear optical properties in solution and in polymethylmethacrylate (PMMA) films, of new nickel heteroleptic Donor-Acceptor dithiolene complexes are reported here ([Ni(Bn 2 pipdt) L1 - 4 ], 1 - 4 ). The acceptor dithione...
Article
Full-text available
Chiral polyamidoamino acids were obtained by polyaddition of N,N'-methylenebisacrylamide with D-, D,L-and L-tryptophan (M-D-Trp, M-D,L-Trp and M-L-Trp). L-tryptophan/glycine copolymers, M-G-L-Trp 5 , M-G-L-Trp 10 , M-G-L-Trp 20 and M-G-L-Trp 40, were prepared from L-tryptophan/glycine mixtures. These polymers were amphoteric, with acid-base propert...
Article
Full-text available
The linear and second-order nonlinear optical (NLO) properties of two pyrene-pyridine chromophores, namely, 4-(pyren-1-yl)pyridine (L1) and 4-(2-(pyren-1-yl)ethyl)pyridine (L2), were investigated and modulated by performing protonation/deprotonation cycles or by complexation to d10 metal centers such as Zn(II) and Cu(I) to form the monomeric [Zn(CH...
Article
Cyclic triimidazole (C9H6N6, L), with C3h molecular symmetry and three nitrogen atoms available for coordination, is here successfully employed for the first time in the synthesis of coordination compounds. In particular, by varying the reaction conditions (e.g. solvent, temperature, template), seven Cu(I)-halide coordination polymers of different...
Article
Four coordination compounds [Zn3(CH3COO)6(H2O)2](TT)2 [Cd(H2O)6](ClO4)2(TT)2, [Cd(H2O)6](BF4)2(TT)2, [Zn(H2O)6](BF4)2(TT)2 (1‐4) accommodating the crystallization induced emissive triimidazo[1,2‐a:1’,2’‐c:1’’,2’’‐e][1,3,5]triazine (TT) as a guest in their crystal lattice are isolated and fully photophysically and structurally characterized. Their e...
Article
Since heavy halogen atoms can be used to tune the emissive properties of organic luminogens, the understanding of their role in the photophysics is fundamental for materials engineering. Here, the extrinsic and intrinsic heavy atom effects on the photophysics of organic crystals are separately evaluated by comparing cyclic triimidazole (TT) with it...
Article
The understanding of the mechanisms involved in crystal packing effects on the photophysical properties of a molecular entity is fundamental to engineer solid materials for specific applications. In fact, besides rigidification and protection from oxygen quenching, crystal packing influences the emissive properties through specific interactions. In...
Article
We disclose a new family of photochromic cyclometalated platinum(II) complexes (PtDTE1 and PtDTE2), where a dithienylethene (DTE) unit is connected at the para-position of the central phenyl ring of (N^C^N) cyclometalated ligand, through two different linkages. Their syntheses are presented along with the X-ray characterizations of both the open an...
Article
Solid luminogens' performances are determined by both their inherent electronic properties and packing status. Intermolecular interactions have been exploited to produce persistent room-temperature phosphorescence (RTP) from organic molecules. However, the design of organic materials with bright RTP and the rationalization of the role of interchrom...
Article
On the way to copper(I) iodide coordination polymers with specific luminescent properties, the in situ reduction of Cu(II) in the presence of KI and bidentate N-heteroatomic ligand, either pyrazine (pyz) or 4,4'-bipyridine (bpy), resulted in one two-dimensional and two three-dimensional new coordination networks. Starting from Cu(NO3)2·3H2O in the...
Article
Solid state luminescent materials with long lifetimes are the subject of ever growing interest both from a scientific and a technological point of view. However, when dealing with organic compounds, the achievement of highly efficient materials is limited by aggregation caused quenching (ACQ) phenomena on one side and by ultrafast deactivation of t...
Article
Two novel green β-substituted Zn(II)-porphyrins, G1 and G2, based on a 4D-π-1A type substitution pattern have been synthesized. Their enhanced push-pull character, by reduction of H-L energy gaps, promotes broadening and red-shifting of absorption bands. The effective synthetic pathway and the remarkable spectroscopic properties make G2 ideal for B...
Article
A film of [Pd(R2pipdt)(dmit)] (1), where R2pipdt = 1,4-didodecyl-piperazine-2,3-dithione (acceptor) and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate (donor) incorporated into a polymethylmethacrylate (PMMA) matrix, showing a good second-harmonic generation, has been prepared for the first time in the class of dithione–dithiolate 2nd order NLO-chromo...
Article
A novel square-planar diimine-dithiolate nonlinear optical (NLO) chromophore, the complex [Ni(o-phen)(bdt)] (1), is reported in this paper (o-phen = dianion of 1,2-phenylendiamina; bdt =1,2-benzenedithiolate). This compound has been fully characterized by single-crystal X-ray diffraction, UV-vis-NIR spectroscopy, cyclic voltammetry, DFT, and TD-DFT...
Article
Inorganic-organic hybrid materials have shown excellent optoelectronic device performances from single-layer solution-processed thin films. Their electronic bands are coupled to the ionic interactions within the organic and inorganic moieties. Exactly these features also allow a sequential deposition route so as to implement thin films having inher...
Article
The first example of a Y-shaped ferrocene quinoxaline derivative with a surprisingly high and stable second harmonic generation (SHG) response in composite polymeric films is reported. The interesting quadratic hyperpolarizability values of different substituted Y-shaped chromophores are also investigated in solution by the EFISH technique.
Article
Full-text available
This work reports on the design, synthesis and photo-physical properties of two ruthenium σ-alkynyl complexes. It is shown that, despite similar optical absorption features recorded in solution, the introduction of a benzaldehyde moiety leads to an improved non-linear optical (NLO) response as measured by Electric Field Induced Second Harmonic (EFI...
Article
The synthesis and second-order nonlinear optical (NLO) properties of seven novel fullerene-C-60 derivatives are reported. In these donor bridge acceptor systems, the fullerene unit (acceptor) is connected through a cyclopropane ring to an ethynyl thienyl fragment (bridge) which binds a trimethylsilyl or platinum alkynyl fragment (donor). All deriva...
Article
The introduction of alkoxy chains in the molecular architecture of meso push-pull porphyrins is of paramount importance aiming at high performing dye-sensitized solar cells (DSSCs) based on these specific sensitizers. Recently, we have demonstrated that the same approach is fruitful even if it is applied to tetraarylporphyrins with an acceptor/anch...
Article
Full-text available
A comprehensive optical investigation of 1,1-dicyano-2,2-bis(4-dimethylaminophenyl)ethylene (1) is presented. The compound crystallizes in four different forms all displaying AIE behavior. The crystalline forms A and B are yellow-orange-emissive, while C and D are green-emissive. On the basis of X-ray structural analysis, the weak intermolecular in...
Article
Full-text available
The acidochromic behaviour of trans-5-(p-(N,N-diphenylamino)styryl)-1,3-di(2-pyridyl)benzene (1) and 5-(p-(N,N-diphenylamino)phenylethynyl)-1,3-di(2-pyridyl) benzene (2) was investigated, both in solution and doped into films, studying their linear and nonlinear optical properties. Remarkably, the efficient luminescence of 1 drops drastically upon...
Article
The continuous search for hybrid inorganic-organic compounds to be used in a variety of applications points obviously to the abundant, cheap, and environmental friendly copper. Cu(I) complexes exhibit a high structural diversity and are emissive with several classes of ligands with properties varying markedly with structure and environment. Solid s...
Article
Full-text available
An unprecedented DTE-based Pt(II) complex, 2(o), stands as the first example of a sequential double nonlinear optical switch, induced first by protonation and next upon irradiation with UV light.
Article
Full-text available
Polyaniline and poly(4-aminodiphenyl)aniline have been prepared following two different synthetic protocols (a traditional method and a “green” method). Both the polymers have been spin coated with salicylic acid and 5-sulfosalicylic acid as the dopants, in order to obtain them in form of thin films. These materials have been characterized, thereof...
Article
The unexpected and acido-triggered reversible luminescent and nonlinear optical properties of (2-pyrene-1-yl-vinyl)pyridine, a simple and highly transparent chromophore, are studied both in solution and in the solid state. Remarkably, for the first time the acidomodulation of the NLO response of a poled thin film is reported.
Article
Full-text available
A poly(methyl methacrylate) (PMMA) composite film containing 4 wt% of the strongly second order NLO active ionic material [(E)-N,N-dimethylamino-N’-methylstilbazonium][p-toluenesulfonate] (DAST) deposited on ITO substrate shows by a two step process (electric poling followed by controlled thermal annealing) a nonlinear optical coefficient d33 highe...
Article
The unexpectedly high quadratic hyperpolarizability values of simple Ru and Pt alkynyl complexes have been measured by the EFISH technique, and this prompted us to investigate their potential as molecular building blocks for composite films with second harmonic generation properties.
Article
Novel photochromic dithienylethene-based platinum(II) complexes (C^N^N)Pt(C≡C-DTE-C6H4-D) ((C^N^N) = 4,4'-di(n-hexyl)-6-phenyl-2,2'-bipyridine; D = H, NMe2) were prepared and characterized. Their excellent photochromic properties allow the photo-induced switching of their second-order nonlinear optical properties in solution, as measured by the EFI...
Article
We studied the second-order NLO properties in solution of various Ir(III) acetylacetonate complexes bearing a substituted cyclometallated 4-styryl-2-phenylpyridine (ppy-4-styryl-R, with R = NEt2, OMe, H, NO2) with the EFISH technique. The dipole moments were evaluated by Density Functional Theory (DFT) calculations. We have also investigated the Se...
Article
The second-order nonlinear optical (NLO) properties of various Pt(II) acetylcetonate complexes bearing a substituted cyclometalated 4-styryl-2-phenylpyridine (ppy-4-styryl-R, with R = NEt 2 , OMe, H, NO 2) were investigated in DMF solution on working with an incident wavelength of 1907 nm by the EFISH technique, whereas the dipole moments were dete...
Article
The photoswitching of the second harmonic generation signal of poled phenyl-substituted dithienylethene/polystyrene thin films evidence a different behavior in function by their molecular structure. The three nonzero χXXZ(2), χZXX(2), and χZZZ(2) coefficients of second order susceptibility at 1064 nm have been measured for both isomeric forms of su...
Article
A poly(methyl methacrylate) (PMMA) composite film containing 4 wt% of the strongly second order NLO active ionic material [(E)-N,N-dimethylamino-N′-methylstilbazonium][Cu5I6] (1), obtained by spin coating of a CH3CN solution on a glass substrate, shows by a two step process (electric poling followed by controlled thermal annealing up to 140 °C) in...
Article
The “swelling–poling–deswelling” technique is a new procedure of poling crosslinked polymeric network carrying covalently attached NLO (nonlinear optical) chromophores. It is based upon a solvent-swollen crosslinked polymeric network before submission to poling. Under electrical poling, the matrix is deswelled without heating above the polymer Tg (...
Article
In this work, the second harmonic generation (SHG) and the nonlinear optical (NLO) coefficients d33 of PMMA films, containing 4 wt % NLO active macrocyclic chromophores based on a cyclotetrasiloxane scaffold and of their monomeric structurally homologous NLO active chromophores, were obtained by an electrical poling process and measured at room tem...
Article
Full-text available
New swellable cyclodextrin-based poly(amidoamine) nanosponges, named PAA-NS10 and PAA-NS11, were synthesized by crosslinking β-cyclodextrin with either 2,2-bisacrylamidoacetic acid or with polyamidoamine segments deriving from 2,2-bisacrylamidoacetic acid and 2-methylpiperazine, respectively. Water uptake studies showed a tremendous swelling capaci...
Article
Poly(methyl methacrylate) (PMMA) films with 4 wt% of the ionic second order NLOchromophore[(E)-N,N-dimethylamino-N′-methylstilbazolium][p-toluenesulfonate] (DAST), obtained by spin-coating of CHCl3–CH3OH (2/1) solutions, show in situ growth of homogeneously dispersed oriented nanocrystals with sizes of less than 100 nm, as supported by TEM and GIXR...
Article
An original and convenient three steps (swelling–poling–deswelling) process of poling a cross-linked polymer/NLO-phore composite to produce a stable second harmonic generation is described, using as a model system a cross-linked poly-amido amine network carrying covalently attached a modified Disperse Red One, a well known NLO-phore. This procedure...
Article
We report on excited state dynamics in isolated poly(9,9-dioctylfluorene) chains obtained by embedding the polymer in an inert plastic matrix. Early events (<300 fs) of intrachain photophysics are detected by pump-probe spectroscopy using tunable UV 25-fs pump pulses and sub-10-fs visible probe pulses. We show that higher-lying optical states, reac...
Article
Using ultrafast spectroscopy, we report evidence of monodimensional photophysics coming from isolated chains of poly(9,9-dioctylfluorene) dispersed in a polymethylmethacrylate matrix. We identify intrachain charge carriers dynamics, the decay taking place in about 1 ps. Using a three-pulse experiment we bring evidence for charges generation from hi...
Article
Using ultrafast pump-probe and pump-push-probe spectroscopy we highlight evidence of monodimensional photophysics coming from isolated chains of poly(9,9-dioctylfluorene) (PFO). We identify a large gain band with peak value of 2600 db/cm. By exploiting the peculiar one-dimensional physics of the isolated chain, we envisage a novel principle for ult...

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