Poly(2,5-bis(2-octyldodecyl)-3,6-di(furan-2-yl)-2,5-dihydro-pyrrolo[3,4-c] pyrrole-1,4-dione-co-thieno[3,2-b]thiophene): A high performance polymer semiconductor for both organic thin film transistors and organic photovoltaics

A new diketopyrrolopyrrole (DPP)-containing donor-acceptor polymer, poly(2,5-bis(2-octyldodecyl)-3,6-di(furan-2-yl)-2,5-dihydro-pyrrolo[3,4-c] pyrrole-1,4-dione-co-thieno[3,2-b]thiophene) (PDBF-co-TT), is synthesized and studied as a semiconductor in organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). High hole mobility of up to 0.53 cm 2 V -1 s -1 in bottom-gate, top-contact OTFT devices is achieved owing to the ordered polymer chain packing and favoured chain orientation, strong intermolecular interactions, as well as uniform film morphology of PDBF-co-TT. The optimum band gap of 1.39 eV and high hole mobility make this polymer a promising donor semiconductor for the solar cell application. When paired with a fullerene acceptor, PC 71BM, the resulting OPV devices show a high power conversion efficiency of up to 4.38% under simulated standard AM1.5 solar illumination.

3,6-Di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione and bithiophene copolymer with rather disordered chain orientation showing high mobility in organic thin film transistors

Pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione or diketopyrrolopyrrole (DPP) is a useful electron-withdrawing fused aromatic moiety for the preparation of donor-acceptor polymers as active semiconductors for organic electronics. This study uses a DPP-furan-containing building block, 3,6-di(furan-2-yl)pyrrolo[3,4- c]pyrrole-1,4(2H,5H)-dione (DBF), to couple with a 2,2′-bithiophene unit, forming a new donor-acceptor copolymer, PDBFBT. Compared to its structural analogue, 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBT), DBF is found to cause blue shifts of the absorption spectra both in solution and in thin films and a slight reduction of the highest occupied molecular orbital (HOMO) energy level of the resulting PDBFBT. Despite the fact that its thin films are less crystalline and have a rather disordered chain orientation in the crystalline domains, PDBFBT shows very high hole mobility up to 1.54 cm 2 V-1 s-1 in bottom-gate, top-contact organic thin film transistors.

Solution processable poly(2,5-dialkyl-2,5-dihydro-3,6-di-2-thienyl- pyrrolo[3,4-c]pyrrole-1,4-dione) for ambipolar organic thin film transistors

Solution processable diketopyrrolopyrrole (DPP)-bithiophene polymers (PDBT) with long branched alkyl side chains on the DPP unit are synthesized. These polymers have favourable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for the injection and transport of both holes and electrons. Organic thin film transistors (OTFTs) using these polymers as semiconductors and gold as source/drain electrodes show typical ambipolar characteristics with very well balanced high hole and electron mobilities (μ h = 0.024 cm 2 V -1 s -1 and μ e = 0.056 cm 2 V -1 s -1). These simple and high-performing polymers are promising materials for ambipolar organic thin film transistors for low-cost CMOS-like logic circuits.

Peripherally η1-Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays

The modification of peripherally metalated meso-η1-platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh3)2] (H2DAPP = 5-phenyl-10,20-bis(3‘,5‘-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4‘-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV−visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.

Le infrastrutture viarie dismesse o declassate ed il progetto di paesaggio

Paesaggio ed infrastrutture viarie sono un binomio molto forte: il primo ha insito il concetto di accessibilità, in quanto non può esistere senza la presenza di un osservatore; la strada, invece, trova i fattori che la connotano nel suo rapporto con la morfologia su cui insiste. Le infrastrutture viarie sono elemento strutturale e strutturante non solo di un territorio, ma anche di un paesaggio. Le attuali esigenze di mobilità portano oggi a ripensare ed adeguare molte infrastrutture viarie: laddove è possibile si potenziano le strutture esistenti, in diversi casi si ricorre a nuovi tracciati o a varianti di percorso. Porsi il problema di conservare itinerari testimoni della cultura materiale ed economica di una società implica considerazioni articolate, che travalicano i limiti del sedime: una via è un organismo più complesso della semplice linea di trasporto in quanto implica tutta una serie di manufatti a supporto della mobilità e soprattutto il corridoio infrastrutturale che genera e caratterizza, ovvero una porzione variabile di territorio definita sia dal tracciato che dalla morfologia del contesto. L’evoluzione dei modelli produttivi ed economici, che oggi porta quote sempre maggiori di popolazione a passare un tempo sempre minore all’interno del proprio alloggio, rende la riflessione sulle infrastrutture viarie dismesse o declassate occasione per la progettazione di spazi per l’abitare collettivo inseriti in contesti paesaggistici, tanto urbani che rurali, tramite reti di percorsi pensate per assorbire tagli di mobilità specifici e peculiari. Partendo da queste riflessioni la Tesi si articola in: Individuazioni del contesto teorico e pratico: Lo studio mette in evidenza come la questione delle infrastrutture viarie e del loro rapporto con il paesaggio implichi riflessioni incrociate a diversi livelli e tramite diverse discipline. La definizione dello spazio fisico della strada passa infatti per la costruzione di un itinerario, un viaggio che si appoggia tanto ad elementi fisici quanto simbolici. La via è un organismo complesso che travalica il proprio sedime per coinvolgere una porzione ampia di territorio, un corridoio variabile ed articolato in funzione del paesaggio attraversato. Lo studio propone diverse chiavi di lettura, mettendo in luce le possibili declinazioni del tema, in funzione del taglio modale, del rapporto con il contesto, del regime giuridico, delle implicazioni urbanistiche e sociali. La mobilità dolce viene individuata quale possibile modalità di riuso, tutela e recupero, del patrimonio diffuso costituito dalle diversi reti di viabilità. Antologia di casi studio: Il corpo principale dello studio si basa sulla raccolta, analisi e studio dello stato dell’arte nel settore; gli esempi raccolti sono presentati in due sezioni: la prima dedicata alle esperienze più significative ed articolate, che affrontano il recupero delle infrastrutture viarie a più livelli ed in modo avanzato non concentrandosi solo sulla conversione del sedime, ma proponendo un progetto che coinvolga tutto il corridoio attraversato dall’infrastruttura; la seconda parte illustra la pratica corrente nelle diverse realtà nazionali, ponendo in evidenza similitudini e differenze tra i vari approcci.

Assetti proprietari e meccanismi di governance nelle imprese familiari [Finacial reporting in small family firms : searching for a new framework]

SOMMARIO: 1. La “governance” nelle aziende familiari: rilevanza, aspetti distintivi e criticità. 2. Il ruolo della compagine proprietaria nella definizione dei meccanismi di governo. 3. Composizione e funzioni del consiglio d’amministrazione. 4. I patti di famiglia come strumento di disciplina dei rapporti impresa-famiglia. 5. Considerazioni conclusive: prospettive di analisi e scenari futuri negli studi sulla governance delle imprese familiari.

L'informativa di bilancio nelle imprese familiari di piccole dimensioni : caratteri distintivi e aspetti evolutivi

SOMMARIO: 1. I fattori che incidono sulla funzione informativa del bilancio nelle imprese familiari. 2. Funzione, obiettivi e attese informative nella comunicazione esterna delle imprese familiari. 3. I caratteri del “familismo” nei prospetti di bilancio. 4. Verso un nuovo modello di bilancio per le imprese familiari: riflessioni critiche e spunti per la ricerca.

An infrared study of adsorption of paranitrophenol on mono, di and trialkyl surfactant intercalated organoclays

Infrared spectroscopy has been used to study the adsorption of paranitrophenol on mono, di and tri alkyl surfactant intercalated montmorillonite. Organoclays were obtained by the cationic exchange of mono, di and tri alkyl chain surfactants for sodium ions [hexadecyltrimethylammonium bromide (HDTMAB), dimethyldioctadecylammonium bromide (DDOAB), methyltrioctadecylammonium bromide (MTOAB)] in an aqueous solution with Na-montmorillonite. Upon formation of the organoclay, the properties change from strongly hydrophilic to strongly hydrophobic. This change in surface properties is observed by a decrease in intensity of the OH stretching vibrations assigned to water in the cation hydration sphere of the montmorillonite. As the cation is replaced by the surfactant molecules the paranitrophenol replaces the surfactant molecules in the clay interlayer. Bands attributed to CH stretching and bending vibrations change for the surfactant intercalated montmorillonite. Strong changes occur in the HCH deformation modes of the methyl groups of the surfactant. These changes are attributed to the methyl groups locking into the siloxane surface of the montmorillonite. Such a concept is supported by changes in the SiO stretching bands of the montmorillonite siloxane surface. This study demonstrates that paranitrophenol will penetrate into the untreated clay interlayer and replace the intercalated surfactant in surfactant modified clay, resulting in the change of the arrangement of the intercalated surfactant.

Poly[di-mu-aqua-bis(mu-2-amino-4-nitrobenzoato)dicaesium]

In the structure of title compound [Cs2(C7H5N2O4)2(H2O)2]n the asymmetric unit comprises two independent and different Cs centres, one nine-coordinate, the other seven coordinate, with both having irregular stereochemistry. The CsO9 coordination comprises oxygen donors from three bridging water molecules, one of which is doubly bridging, three from carboxylate groups, and three from nitro groups, of which two are bidentate chelate bridging. The CsO6N coordination comprises the two bridging water molecules, one amine N donor, one carboxyl O donor and four O donors from nitro groups (two from the chelate bridges). The extension of the dimeric unit gives a two-dimensional polymeric structure which is stabilized by both intra- and intermolecular amine N-H...O and water O-H...O hydrogen bonds to carboxyl O acceptors, as well as inter-ring pi-pi interactions [minimum ring centroid separation, 3.4172(15)A].

Bayesian models for the determination of resonant frequencies in a DI diesel engine

A time series method for the determination of combustion chamber resonant frequencies is outlined. This technique employs the use of Markov-chain Monte Carlo (MCMC) to infer parameters in a chosen model of the data. The development of the model is included and the resonant frequency is characterised as a function of time. Potential applications for cycle-by-cycle analysis are discussed and the bulk temperature of the gas and the trapped mass in the combustion chamber are evaluated as a function of time from resonant frequency information.

Homo- and heteronuclear meso,meso-(E)-Ethene-1,2-diyl-Linked Diporphyrins : preparation, X-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Absence of intersystem crossing in 1,4-didehydrobenzene

The rate of singlet-to-triplet intersystem crossing in 1,4-didehydrobenzene (the biradical produced as a reactive intermediate in the thermal cycloaromatization of enediynes), cannot be increased by the application of an external magnetic field. The rate of product formation and the distribution of stable products of 2,3-di-n-propyl-1,4-didehydrobenzene thermolysis is unchanged at magnetic flux densities in the range 0–2000 G and at 66 000 G. Similarly, the rate of thermolysis of an unsymmetrical enediyne is insensitive to magnetic field flux in the same range. This finding precludes the modulation of enediyne reaction rates in pharmaceutical and synthetic pursuits.