Abstract
La síntesis de derivados terpiridinicos (Tpy) se ha investigado ampliamente debido a su potencial para la conversión de energía solar. En este artículo se sintetizó y caracterizó el 4-([2,2':6',2'' terpiridin]-4'-il)fenol (TpyOH), a través de varias metodologías como la cristalografía de rayos X y herramientas computacionales. El análisis de rayos X de monocristal mostró que el TpyOH es plano, con ángulos diedros de 5,03° entre el piridinilo central y el anillo fenólico, con presencia de ángulos de 6,05 y 12,2º en la porción terpiridínica. En el cristal, las moléculas están unidas por enlaces de hidrógeno intermoleculares y mediante interacciones de apilamiento π-π. Utilizando cálculos DFT dependientes del tiempo (TD-DFT) y teniendo en cuenta el efecto de los disolventes, se investigaron y compararon los espectros de absorción y fluorescencia de TpyOH. Las energías de transición TD-DFT de S0→Sn y S1→S0 concuerdan con los resultados experimentales. El análisis de orbitales moleculares de frontera mostró que la banda de absorción de baja energía corresponde a transferencia de carga intraligando (ICT); mientras que la banda de alta energía es común en las transiciones π-π* del resto Tpy. La emisión debido a la transición S1→S0 corresponde a ICT, con una contribución del 90% proveniente de transiciones HOMO→LUMO.
Highlights
Wn this contributionC the .Nk[vCvöSFöCvööNterpyridin]N.öNylXphenol compound was synthesized in a moderate yield following the *rönhke conditions and its structure was unambiguously determined by XNray singleNcrystal diffractionC V;N and Vq–NNMRC and UVNvis techniquesM –rystallographic and LAT results showed that the transoid conformation kTpyO; V isomerX corresponds to the most stable and predominant structure for the model compoundM –omparison between the geometrical parameters of the optimized ground state and the crystal data shows that the differences are related to the intermolecular hydrogen bond formed between two adjacent molecules in the crystal packingM
ConclusionAcknowledgmentsWn this contributionC the .Nk[vCvöSFöCvööNterpyridin]N.öNylXphenol compound was synthesized in a moderate yield following the *rönhke conditions and its structure was unambiguously determined by XNray singleNcrystal diffractionC V;N and Vq–NNMRC and UVNvis techniquesM –rystallographic and LAT results showed that the transoid conformation kTpyO; V isomerX corresponds to the most stable and predominant structure for the model compoundM –omparison between the geometrical parameters of the optimized ground state and the crystal data shows that the differences are related to the intermolecular hydrogen bond formed between two adjacent molecules in the crystal packingMThe SU→Sn and SV→SU transition energies calculated with the P–MRTLNPx9URFqV3YkdCpX level of theory are in good agreement with experimental resultsM TLNPx9U results show that both the absorption band observed in the qqU–.VU nm range and the emission band have their main contribution from the ;OMO to the LUMO orbitals and are assigned as intraligand charge transfer kW–TX transitionsMAor financial supportC we are thankful to –olciencias kYrants Dq.NvUVV and VVVOFDO.qTqjX and to Lireccion Nacional de WnvestigacionesNUNGL kYrant VOvjFXM
Summary
] síntese de derivados de terpiridina 8/pyA tem sido estudada devido ao seu potencial para a conversão de energia solarE çesta contribuição o aF8[373-w@-73--F terpiridina]Fa-FilA fenol 8/pyâ%A foi sintetizado caracterizado e estudado por vários métodosE ] análise de estrutura de raios X de cristal único mostra que o /pyâ% é plano com ângulos diedros de :7y0 ° entre o piridinilo central e o anel fenólico e também @7y: e O373 ° na porção de terpiridinaE ço cristal as moléculas são ligadas por ligações intermoleculares de hidrogênio e através de interações de empilhamento πFπE Rsando uma abordagem da teoria funcional da densidade dependente do tempo e levando em consideração os efeitos do solvente em massa foram investigados e comparados os espectros de absorção e fluorescência do /pyâ%E ]s energias de transição /XFXk/ öy→ön e öO→öy estão de acordo com os resultados experimentaisE ] análise de orbitários moleculares de fronteira mostrou que a banda de absorção de baixa energia possui um caráter de transferência de carga intraligando 8/qzA7 enquanto a banda de alta energia é uma característica comum das transições πFπ. da fração /pyE ] transição de emissão öO→öy também tem um caráter /qz com uma contribuição de fy das transições %âãâ→úRãâE. –urrentlyö terpyridines PTpysJ have a very important presence in the scientific literature due principally to their optoelectronic properties and coordination capability P1-3J4 The different characteristics of Tpys are provided by the three neighbouring pyridine rings and their spatial dispositionö which form a very particular and changeable electronic space4 9s a resultö for exampleö Tpys are capable of forming coordination compounds with various transition metals This makes Tpys very promissory moieties in the development of new materials with high technological potentials like photovoltaics P4Jö +UWs P5Jö solar cells P6-9J and chemozsensor probes P10J4. The spatial disposition of the nitrogen atoms over the pyridine rings of Tpys is very important for the physical and chemical properties4 9s a result of the free rotation presented by the sigma bonds that connect the aromatic ringsö Tpys have different structural conformationsö which can present high or low πzelectronic delocalizationö properties that can affect the optoelectronic properties drastically TMnterestinglyö the conformation in Tpys can be altered or modified by specific guestö such as metal ionsö through coordination bonds Thereforeö correlation of spatial conformationsö crystallographic structureö and optoelectronic properties of Tpys are very important for technological applications such as chemical sensors Qereinö the synthesisö characterizationö and the crystal structure of 'zP[IöIM36MöIMMzterpyridin]z'MzylJphenol PTpyOQJ are reportedö a versatile tridentate ligand which may be used as buildingz block for the synthesis of multicomponent systems with interesting photochemical and photophysical properties
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