Phosphorus‐nitrogen compounds. Part 39. Syntheses and Langmuir‐Blodgett thin films and antimicrobial activities of N/N and N/O spirocyclotriphosphazenes with monoferrocenyl pendant arm

Abstract

The Cl substitution reactions of the N/N (1-3) and N/O (4 and 5) spirocyclic monoferrocenylphosphazenes with 1,4-dioxa-8-azaspiro [4,5]decane (DASD) produce the mono-(1a-5a), geminal-(1b-5b) and tetrakis-DASD-substituted ferrocenylspirocyclotriphosphazenes (1c-5c). The mono-and geminal-DASDsubstituted phosphazenes have two and one stereogenic P-centers, respectively. The structures of the compounds were established by spectroscopic techniques.The molecular structures of 3a and 2b were evaluated using X-ray crystallography. Additionally, the ultrathin and highly ordered Langmuir-Blodgett (LB) films of 3a and 2b were also prepared. The characterizations of the LB films were done using p-polarized grazing angle (GAIR) and horizontal attenuated total reflectance (HATR) techniques. On the other hand, the antimicrobial activities of the eight phosphazene derivatives against G(+) and G(-) bacteria and fungi were investigated. Furthermore, the interactions between the compounds and plasmid DNA were studied by agarose gel electrophoresis. isomers may cause to the possibilities of optical isomers.On the other hand, phosphazene derivatives and polyorganophosphazenes are very useful compounds in technological and medicinal areas. They are used as flame retardant additives, [5] electrolytes for lithiumion batteries, [6,7] liquid crystals, [8,9] lubricants, [10] fluorescence chemosensor [11,12] and elastomers. [13] Recently, cyclotriphosphazene derivatives have also attracted a quite of interest for the preparation of the selective anticancer agents, [14] antibacterial and antifungal reagents, [15] and biomedical materials such as synthetic bones. [16] Furthermore, the potential anticancer activities of some of the mono and polyamino substituted cyclotriphosphazenes were reported. [17,18] Besides, the ultrathin films of the obtained inorganic or organic compounds have attracted much interest for applications as industrial materials, as well, such as detectors, sensors, and electronic circuit components. [19] The thin films were prepared using a solid substrate with different methods e.g. thermal evaporation, adsorption from solution, electrodeposition, sputtering, self-assembly molecular beam epitaxy, and Langmuir-Blodgett (LB) techniques. [20,21] There is only one report in the literature about the LB thin films of the phosphazene derivatives published by our group. [22] This study focused on the consecutive Cl replacement reactions of the tetrachloro monoferrocenylphosphazenes (1-5) with DASD for the aim of the obtaining of electronrich reservoir phosphazenes. Thereof, the mono-(1a-5a), geminal (1b-5b) and tetra-DASD-substituted (1c-5c) ferrocenylphosphazenes were synthesized by the reaction of 1-5 with DASD. In addition, the successive substitution reactions of Cl atoms from the pendant armed tetrachloroferrocenylphosphazenes (1-5) emerges a number of different possibilities in terms of regio-and stereoisomer selections. Eventually, we strongly stated that these compounds have been synthesized to investigate their biol...

Phosphorus-nitrogen compounds- (Part 50): correlations between structuralparameters for cylophosphazene derivatives containing ferrocenyl pendant arm(s)

“…On the other hand, we also succeeded in the preparation of ultrathin and highly ordered Langmuir-Blodgett films of tetrachloro-, and mono and gem DASD-substituted mono-ferrocenyl cyclotriphosphazenes [40,41]. These compounds are the first phosphazene derivatives prepared as thin films in the literature.…”

“…The substituted phosphazene derivatives were synthesized by stepwise substitutions of partly substituted spiro-mono (I) and spiro-bis (V) ferrocenyl cyclotriphosphazenes which consist of 4 reactive P-Cl units. The reactions of 1 equimolar amount of partly substituted spiro-bis (V) and spiromono (I) ferrocenyl cyclotriphosphazenes with 1 and 2 equimolar amounts of heterocyclic amines (DASD and Pyr) produced corresponding mono heterocyclic amine (DASD) substituted spiro-bis (VI) [35] and spiro-mono (II) [40] and geminal heterocyclic amine (DASD and Pyr) substituted spiro-bis (VII) [35] and spiro-mono (III) [35,40,41] ferrocenyl cyclotriphosphazenes in the presence of NEt 3 in refluxing dry THF. The fully heterocyclic amine [DASD, Pyr, and morpholine (Morp)] substituted spiro-bis (V) [33] and spiro-mono (I) [33,35,52] ferrocenyl cyclotriphosphazenes were prepared by replacing 4 Cl-atoms on partly substituted derivatives (I) and (V), respectively, with excess heterocyclic amines in boiling THF.…”

“…It was found that the systematic variations in the 31 P NMR chemical shifts depend fundamentally on some electronic (electron-releasing and electron-withdrawing capacities of substituent groups), steric (the steric hindrance between the exocyclic groups) and conformational factors, and on the changes in bond lengths and bond angles around the phosphorus atoms [especially endocyclic ( α) and exocyclic ( α ′ ) bond angles] in cyclotriphosphazene derivatives. The current study deals with a number of correlations between structural parameters [e.g., 31 P NMR spectral data and X-ray crystallographic data (endocyclic and exocyclic NPN bond angles, and bond lengths)] in spirocyclic ferrocenyl cyclophosphazenes introduced to the literature from our research group (Table 1) [33][34][35][36][37][38][39][40][41]52]. Therefore the content of this report includes: (i) a brief description of the synthesis methods of 11 different structural types and a total of 28 spirocyclic ferrocenyl phosphazenes with 5-to 7 −membered spiro-rings used for the graph construction, (ii) the relationship between the δ P spiro shifts and the values of electron density transfer parameters ∆(P-N), and (iii) the correlation of δ P spiro shifts and endocyclic ( α) and exocyclic ( α ′ ) NPN bond angles of the compounds.…”

Synthesis and spectroscopic properties of (N/O) mono- and dispirocyclotriphosphazene derivatives with benzyl pendant arms: study of biological activity

“…In the literature, some cis-and trans-dispirophosphazene products have been presented, but dispirocyclotriphosphazene derivatives with pendant arms are less common [25,26]. The isomer distributions, chiralities, and structural and spectral features of dispiro products with pendant arms were determined in these studies.…”

Phosphorus-nitrogen compounds (Part 51): the relationship betweenspectroscopic and crystallographic data of mono- and di-spirocyclophosphazenederivatives with 4-fluoro/nitrophenylmethyl pendant arm/arms

“…In recent years, cyclotri and cyclotetraphosphazenes have started to attract much attention due to their potential stereogenic properties, and biological activities such as antibacterial, antifungal and anti-cancer activities [8][9][10][11][12]. Our group has spent many years on designating and synthesizing novel partly substituted cyclotri and cyclotetraphosphazene derivatives with bidentate ligands {dibenzo-diaza-crown ethers [13][14][15][16][17], dibenzo N 2 O n (n =2-4) [18][19][20][21] and benzo NO [22][23][24][25][26][27][28] donor * Correspondence: sbilge@science.ankara.edu.tr type aminopodands, mono-and bis-ferrocenyldiamines [29][30][31][32][33][34][35][36][37], sodium (ferrocenylmethylamino)-1-alkoxide [38][39][40][41][42][43]}and multidentate N 2 O 2 -donor type dibenzo aminopodands [44][45][46]. Some interesting phosphazene derivatives such as monotopic and ditopic spiro-crypta phosphazenes, spirocyclic phosphaza (PNP-lariat) ethers, cyclophosphazenes possessing 6-membered spiro ring/rings, mono and bisferrocenylspirocyclophosphazenes, and spiro-ansa-spiro-, spiro-bino-spiro-and ansa-spiro-ansa-phosphazenes were synthesized.…”