سنتز و بررسی ساختار ترکیبات کوئوردیناسیونی جدید سرب (II)با بعضی از لیگاندهای دهنده اکسیژن، نیتروژن و گوگرد و بررسی امکان تهیه ترکیبات نانو از آنها
/بابک میرتمیزدوست
چاپی
دکتری
شیمی معدنی
۱۳۹۱/۰۸/۱۵
:ترکیبات کوئوردیناسیونی جدید سرب (II)با لیگاند هایی از مشتقات۱ و۱۰-فنانترولین و آنیون های شامل آزید، نیترات، استات، یدید، تترافلوئوروبورات سنتز و به وسیله آنالیز عنصری وIR - FTشناسایی و پایداری حرارتی آن ها مطالعه شدند .ساختار کمپلکس های)NO۳)]n (۱)-N۳)(- [Pb(dmp)،)N۳)۲]n (۳)- [Pb(dmp)،[Pb(dmp)I۲]n(۵) ،)ClO۴)۲]n (۷)-N۳)۲(- [Pb۲(dmp)۲،[Pb(phen)۲(NO۳)]BF۴n(۹) ،)CH۳COO)۲](BF۴)۲n (۱۱) - [Pb۲(phen)۲به وسیله پراش پرتو- Xتعیین شدند .همچنین نانو لایه های گل مانند کمپلکس)NO۳)]n(۲)-N۳)(- [Pb(dmp)، نانو میله های شش ضلعی کمپلکس)N۳)۲]n(۴)- [Pb(dmp)، نانو صفحات کمپلکس[Pb(dmp)I۲]n(۶) ، نانو میله های کمپلکس)ClO۴)۲]n (۸)-N۳)۲(- [Pb۲(dmp)۲، نانو ذرات کمپلکس [Pb(phen)۲(NO۳)]BF۴n (۱۰) و)CH۳COO)۲](BF۴)۲n (۱۲) - [Pb۲(phen)۲به روش اولتراسونیک سنتز شدند و شکل ظاهری و مطالعات ساختاری آن ها با استفاده از میکروسکوپ الکترونی روبشی (SEM)و پراش پرتو- Xپودری (PXRD) انجام گرفت .مطالعات ساختاری نشان می دهد تحت تاثیر یون های همراه متفاوت، در ترکیب ۹ کمپلکس تک هسته ای و در بقیه ترکیبات به صورت پلیمر کوئوردیناسیونی یک بعدی تشکیل می شو .ترکیب کوئوردیناسیونی جدیدی از سرب (II)و لیگاندی از مشتقات -دی کتون ها و لیگاند آزو آروماتیک۴ و۷-دی فنیل-۱و۱۰-فنانترولین سنتز و به وسیله آنالیز عنصری CHNوIR - FTشناسایی و پایداری حرارتی آن مطالعه شد .ساختار کمپلکس [Pb(tftb)۲(dpp)۲] (۱۳) به روش پراش پرتو- Xتعیین شد .همچنین به روش ترمولیز در دما های کنترل شده نانواکسید سرب (II)از آن سنتز گردید .توازن بین بر هم کنش های تغییر پذیر از قبیل CFHC و stacking و هم چنین جفت الکترون غیر پیوندی سرب (II)در شکل گیری شبکه کمپلکس نقش موثری داشته است .عدد کوئوردیناسیون این ترکیبات که به جز ترکیب(۱۱) ، شش بوده و کره کوئوردیناسیونی سرب (II)حالت نا متقارن دارد .در ترکیب (۱۱) عدد کوئوردیناسیون سرب (II)هشت است و کره کوئوردیناسیونی سرب (II)حالت نا متقارن دارد
New lead(II) coordination compounds with 1,10-phenanthroline derived ligands and containing different anions such as azide, nitrate, acetate, iodide and tetrafluoroborate have been synthesized and characterized by CHN elemental analysis and FT-IR; further, their thermal stabilities were studied. The structures of [Pb(dmp)(?-N3)(?-NO3)]n (1), [Pb(dmp)(?-N3)2]n (3), [Pb(dmp)I2]n (5), [Pb2(dmp)2(?-N3)2(?-ClO4)2]n (7), [Pb(phen)2(NO3)]BF4n (9) and [Pb2(phen)2(?-CH3COO)2](BF4)2n (11) complexes were determined by X-ray diffraction. The [Pb(dmp)(?-N3)(?-NO3)]n (2) nano flower like layers, [Pb(dmp)(?-N3)2]n (4) nano hexagonal rods, [Pb(dmp)I2]n (6) nano layers, [Pb2(dmp)2(?-N3)2(?-ClO4)2]n (8) nano rods, [Pb(phen)2(NO3)]BF4n (10) and [Pb2(phen)2(?-CH3COO)2](BF4)2n (12) nano structures were synthesized by ultrasonic method. The morphology and structural studies of nano compounds were characterized by scanning electron microscopy (SEM) and were studied by powder X-ray diffraction (PXRD). The results showed that the under influence of different counter ions the compound (9) was a mono nuclear complex and the others were in the form of 1D coordination polymers.ew lead(II) coordination compounds with ?-diketonate derived ligand and 4,7-diphenyl-1,10-phenanthroline aza-aromatic moiety have been synthesized and characterized by CHN elemental analysis and FT-IR; their thermal stabilities were also studied. The structure of [Pb(tftb)2(dpp)2] (13) complex was determined by X-ray diffraction and lead(II) oxide nanoparticles were prepared from that by thermolysis at moderate temperatures. The balance of lone pair activity (about Pb2+) and labile interactions such as C-FH-C and ?-? stacking may be important in determining the lattice arrays of this compound. The coordination number of above compounds was six and the coordination spheres of lead(II) ions were asymmetrical, except for compound (11) with coordination number of eight and asymmetrical lead(II) coordination sphere.ive lead(II) complexes with ligands, nicotinohydrazide [Pb2(nh)2(NO3)4CH3OH]n (14), acetohydrazide [Pb(ah)2(NO3)2]n (16), and [Pb3(ah)2I6]n (18), pyridin-2-ylmethanamine [Pb3(p-2ma)3(N3)3(NO3)3]n (20) and benzene-1,4-diamine [Pb2(b-1,4-da)(CH3COO)4]n (22) have been synthesized and characterized by CHN elemental analysis and FT-IR; their thermal stabilities were studied and their structures were determined by X-ray diffraction. In addition to the [Pb2(nh)2(NO3)4CH3OH]n (15), [Pb(ah)2(NO3)2]n (17), [Pb3(ah)2I6]n (19), [Pb3(p-2ma)3(N3)3(NO3)3]n (21) and [Pb2(b-1,4-da)(CH3COO)4]n (23), nano structures were synthesized by ultrasonic method. The morphology and structural studies of nano compounds were observed by scanning electron microscopy (SEM) and were studied by powder X-ray diffraction (PXRD). The results showed that the complex (14) is 3D coordination polymer with coordination number nine, the complex (16) is 1D coordination polymer with coordination number ten, the complex (18) is 2D coordination polymer with coordination numbers six, eight and six for three different lead(II) centers, the complex (20) is 1D coordination polymer with coordination numbers six, seven and six for three different lead(II) centers and the complex (22) is 2D zig-zag coordination polymer with coordination number seven.our new lead(II) complexes with bis(pyridyl) diaza-butadiene derived ligands containing bromide [Pb(1,2-bp-3-mh)Br2]n (24), chloride [Pb2(1,2-bp-3-mh)Cl4]n (26), thiocyanate [Pb2(1,2-bp-3-mh)(SCN)4]n (27) and azide+nitrate anions [Pb2(1,2-bp-4-mh)2(N3)2(NO3)2]n (28) have been synthesized and characterized by CHN elemental analysis and FT-IR; moreover, their thermal stabilities were studied and their structures were determined by X-ray diffraction. The [Pb(1,2-bp-3-mh)Br2]n (25)and [Pb2(1,2-bp-3-mh)(SCN)4]n (28), nano structures were synthesized by ultrasonic method and the lead(II) oxide nanoparticles were prepared by thermolysis of (26) at moderate temperatures. The morphology and structural studies of nano compounds were observed by scanning electron microscopy (SEM) and were studied by powder X-ray diffraction (PXRD). The results showed that the complex (24) is 1D fish-bone coordination polymer with coordination number six. The Pb?N and Pb?Br bonds arrangement in 24 showed that the coordination sphere of lead(II) ions are holodirected. The complexs (26) and (27) are 3D coordination polymers with coordination numbers six and eight respectively. The coordination sphere of lead(II) ions was hemidirected in (26) and hoodirected in (27). The complex (28) is 3D coordination polymer with coordination number eight and symmetrical coordination sphere of lead(II).our lead(II) 1D zig-zag coordination polymers with pyridin-2-ylmethylene-isonicotinohydrazide ligand containing acetate anions [Pb(p-2-minh)(CH3COO)]n (31), nitrate, [Pb(Hp-2-minh)(NO3)2]n (32), chloride, [Pb(Hp-2-minh)Cl2]n (33) and azide [Pb(p-2-minh)N3 H2O]n (34) were synthesized and characterized by CHN elemental analysis and FT-IR, their thermal stabilities were studied and their structures were determined by X-ray diffraction. The [Pb(p-2-minh)N3 H2O]n (35), flower like nano layers were synthesized by ultrasonic method and the lead(II) oxide nanoparticles were prepared by thermolysis of (31), (32) and (33) at moderate temperatures. The morphology and structural studies of nano compounds were observed by scanning electron microscopy (SEM) and were studied by powder X-ray diffraction (PXRD). The coordination number of lead(II) in (32) was eight and for others were six. The coordination sphere of lead(II) ions for all complex are asymmetrical. hree new lead(II) coordination compounds with pyridin-2-yl)ethylidene-isonicotinohydrazide ligand containing acetate anions [Pb(Hp-2-einh)(CH3COO)]n (36), nitrate [Pb(Hp-2-einh)(NO3)2]n (37) and chloride [Pb(Hp-2-einh)Cl2]n (38) were synthesized and characterized by CHN elemental analysis and FT-IR; their thermal stabilities were studied and their structures were determined by X-ray diffraction. The lead(II) oxide nanoparticles were prepared by their thermolysis at moderate temperatures. The morphology and structural studies of nano compounds were observed by scanning electron microscopy (SEM) and were studied by powder X-ray diffraction (PXRD). The compound (36) is 1D zid-zag coordination polymer with coordination number six and symmetrical coordination sphere; the compound (37) was a mono nuclear coordination compound with asymmetrical coordination sphere of lead(II) and the compound (38) is 1D ladder coordination polymer with coordination number seven and holodirected coordination sphere of lead(II)ow lead(II) 1D netted coordination polymers with pyridin-3-ylmethylene-quinoline-2-carbohydrazide ligand containing thiocyanate [Pb(Hp-3-mq-2ch)(SCN)2]n (39) and nitrate anions [Pb(Hp-3-mq-2ch)(NO3)2]n (41) were synthesized and characterized by CHN elemental analysis and FT-IR; further, their thermal stabilities were studied and their structures were determined by X-ray diffraction. The [Pb(Hp-3-mq-2ch)(SCN)2]n (40) nano compounds and [Pb(Hp-3-mq-2ch)(NO3)2]n (42), nano groundnuts structures were synthesized by ultrasonic method. The morphology and structural studies of nano compounds were characterized by scanning electron microscopy (SEM) and were studied by powder X-ray diffraction (PXRD). The coordination number of lead(II) ions in (39) is seven with symmetrical coordination sphere and the coordination number of lead(II) ions in (41) is nine with asymmetrical coordination sphere. The supramolecular architectures were formed via ?-? stacking interactions and other weak interaction.