Polímeros de coordenação à base de cobalto(II) e N,N'-bis(4-piridil)-1,4,5,8-naftaleno diimida como ligante e suas propriedade estruturais, espectroscópicas e fotoelétricas

Polímeros de coordenação têm atraído a atenção de pesquisadores na última década por conta de sua incrível versatilidade e virtualmente infinito número de possibilidades de combinação de ligantes orgânicos e centros metálicos. Estes compostos normalmente herdam as características magnéticas, eletrônicas e espectroscópicas de seus componentes base. Entretanto, apesar do crescente número de trabalhos na área, ainda são raros os polímeros de coordenação que apresentem condutividade elétrica. Para este fim, utilizou-se a N,N\'-bis(4-piridil)-1,4,5,8-naftaleno diimida, ou NDI-py, que pertence a uma classe de compostos rígidos, planares, quimicamente e termicamente estáveis e que já foram extensamente estudados por suas propriedades fotoeletroquímicas e semicondução do tipo n. O primeiro polímero de coordenação sintetizado, MOF-CoNDI-py-1, indicou ser um polímero linear, de estrutura 1D. O segundo, MOF-CoNDI-py-2, que conta com ácido tereftálico como ligante suporte, é um sólido cristalino com cela unitária monoclínica pertencente ao grupo espacial C2/c, determinado por difração de raios-X de monocristal. A rede apresenta um arranjo trinuclear de íons Co(II) alto spin com coordenados em uma geometria de octaedro distorcido, enquanto os ligantes NDI-py se encontram em um arranjo paralelo na estrutura, em distâncias apropriadas para transferência eletrônica. Com o auxílio de cálculo teóricos a nível de DFT, foi realizado um estudo aprofundado dos espectros eletrônicos e vibracionais, com atribuição das transições observadas, tanto para o MOF-CoNDI-py-2 quanto para o ligante NDI-py livre. A rede de coordenação absorve em toda a região do espectro eletrônico analisada, de 200 nm a 2500 nm, além de apresentar luminescência com característica do ligante. Dispositivos eletrônicos fabricados com um cristal do MOF-CoNDI-py-2 revelaram condutividades da ordem de 7,9 10-3 S cm -1, a maior já observada para um MOF. Além de elevada, a condutividade elétrica dos cristais demonstrou-se altamente anisotrópica, sendo significativamente menos condutor em algumas direções. Os perfis de corrente versus voltagem foram analisados em termos de mecanismos de condutividade, sendo melhores descritos por um mecanismo limitado pelo eletrodo to tipo Space-Charge Limited Current, concordando com a proposta de condutividade através dos planos de NDI-py na rede. A condutividade dos cristais também é fortemente dependente de luz, apresentando fotocondução quando irradiado por um laser vermelho, de 632 nm, enquanto apresenta um comportamento fotorresistivo frente a uma fonte de luz branca. Estes resultados, combinados, trazem um MOF em uma estrutura incomum e com elevada condutividade elétrica, modulada por luz, em medidas diretas de corrente. Não existem exemplos conhecidos de MOFs na literatura com estas características.

County Armàgh, Northern Ireland, United Kingdom, 1760 (Image 1 of 4) (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: A topographical map of the county of Armagh to which is anex'd the plans of Newry and Armagh, by John Rocque = Carte topographique de la Province d'Armagh où se trouve les plans des villes d'Armagh et de Newry, par Jean Rocque. It was published by J. Rocque in 1760. Scale [ca. 1:41,000]. This layer is image 1 of 4 total images of the four sheet source map, representing the southeast portion of the map. Covers County Armàgh, Northern Ireland. Map in English and French. The image inside the map neatline is georeferenced to the surface of the earth and fit to the Irish Grid (Transverse Mercator 1965 (TM-65)) coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as roads, drainage, built-up areas and selected buildings, selected names of landowners, ground cover, and more. Relief shown by hachures and pictorially. Includes 2 insets: "A Plan of the Town of Newry" -- "A Plan of the City of Armagh".This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

County Armàgh, Northern Ireland, United Kingdom, 1760 (Image 2 of 4) (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: A topographical map of the county of Armagh to which is anex'd the plans of Newry and Armagh, by John Rocque = Carte topographique de la Province d'Armagh où se trouve les plans des villes d'Armagh et de Newry, par Jean Rocque. It was published by J. Rocque in 1760. Scale [ca. 1:41,000]. This layer is image 2 of 4 total images of the four sheet source map, representing the northeast portion of the map. Covers County Armàgh, Northern Ireland. Map in English and French. The image inside the map neatline is georeferenced to the surface of the earth and fit to the Irish Grid (Transverse Mercator 1965 (TM-65)) coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as roads, drainage, built-up areas and selected buildings, selected names of landowners, ground cover, and more. Relief shown by hachures and pictorially. Includes 2 insets: "A Plan of the Town of Newry" -- "A Plan of the City of Armagh".This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

County Armàgh, Northern Ireland, United Kingdom, 1760 (Image 3 of 4) (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: A topographical map of the county of Armagh to which is anex'd the plans of Newry and Armagh, by John Rocque = Carte topographique de la Province d'Armagh où se trouve les plans des villes d'Armagh et de Newry, par Jean Rocque. It was published by J. Rocque in 1760. Scale [ca. 1:41,000]. This layer is image 3 of 4 total images of the four sheet source map, representing the southwest portion of the map. Covers County Armàgh, Northern Ireland. Map in English and French. The image inside the map neatline is georeferenced to the surface of the earth and fit to the Irish Grid (Transverse Mercator 1965 (TM-65)) coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as roads, drainage, built-up areas and selected buildings, selected names of landowners, ground cover, and more. Relief shown by hachures and pictorially. Includes 2 insets: "A Plan of the Town of Newry" -- "A Plan of the City of Armagh".This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

County Armàgh, Northern Ireland, United Kingdom, 1760 (Image 4 of 4) (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: A topographical map of the county of Armagh to which is anex'd the plans of Newry and Armagh, by John Rocque = Carte topographique de la Province d'Armagh où se trouve les plans des villes d'Armagh et de Newry, par Jean Rocque. It was published by J. Rocque in 1760. Scale [ca. 1:41,000]. This layer is image 4 of 4 total images of the four sheet source map, representing the northwest portion of the map. Covers County Armàgh, Northern Ireland. Map in English and French. The image inside the map neatline is georeferenced to the surface of the earth and fit to the Irish Grid (Transverse Mercator 1965 (TM-65)) coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as roads, drainage, built-up areas and selected buildings, selected names of landowners, ground cover, and more. Relief shown by hachures and pictorially. Includes 2 insets: "A Plan of the Town of Newry" -- "A Plan of the City of Armagh".This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Medicus microcosmus seu spagyria microcosmi : exhibens medicinam corpore hominis túm vivo, tùm extincto doctè eruendam ... /

Mode of access: Internet.

Resolutionum quotidianarum iuris Pontificij, Caesarei, & regni Neapolis liber primus : in quo variae, et multiplices materiae tàm ecclesiasticae, quam prophanae in vtroquè foro frequentiùs occurrentes, vtilitèr, ac singulari methodo resoluuntur .../

Mode of access: Internet.

Technical manual, unit maintenance : truck, utility, cargo/troop carrier, 1-1/4 ton, 4x4, M998 (2320-01-107-7155) ... truck, ambulance, 2-litter, soft top, 4x4, M1035 (2310-01-146-7194).

Includes index.

Unit, direct support, and general support maintenance repair parts and special tools lists for crane, wheel-mounted, 4-ton, self-propelled for aircraft maintenance and positioning (SCAMP), Grove Manufacturing Company model RT 41AA (NSN 3810-01-144-4885).

"May 1992."

Unit, direct support, and general support maintenance repair parts and special tools lists (including depot maintenance repair parts and special tools lists) : mixer, rotary tiller, DED, 4 wheel, pneumatic tired, self-propelled, NSN 3895-00-883-0437, FWD Corporation model B2-ll7l.

"June 1992."

Unit, direct support, and general support maintenance repair parts and special tools lists (including depot maintenance repair parts and special tools lists) : crane-shovel, crawler mounted, diesel engine driven, 12-1/2 ton capacity, rated with 3/4 cu yd (NSN 3810-00-937-3939), Thew-Lorain model L-36M.

"August 1992."