UB-Vis Spektroskopiya — Birikmalar Katalogi

Nazariya Sahifasi
Jami birikmalar
25
d–d o'tishli
17
CT (LMCT / MLCT)
10
Rangsiz (d⁰, d¹⁰)
2
O'tish turi:
Tag:

25 ta birikma topildi

[Co(NH3)6]Cl3

Geksaamminkobalt(III) xlorid

Luteo-kobalt (sariq)

Konfiguratsiya
d⁶ LS
Yer holati
¹A₁g
Rang:sariq-to'q sariq
Struktura:Oktaedr (Oh)
Markazi:Co³⁺
Magnit:Diamagnit

Asosiy o'tishlar:

475 nmd-d
¹A₁g → ¹T₁gε=60
340 nmd-d
¹A₁g → ¹T₂gε=55
Δo
22,900
cm⁻¹
Racah B (β=0.66)
615
cm⁻¹

Werner klassikasi, past spin

klassikinertd⁶ LSOh
M = 267.48 g/molBatafsil →

[Co(NH3)5Cl]Cl2

Pentaamminklorokobalt(III) xlorid

Purpureo-kobalt (binafsha)

Konfiguratsiya
d⁶ LS
Yer holati
¹A₁
Rang:binafsha-qizil
Struktura:Oktaedr (C₄ᵥ)
Markazi:Co³⁺
Magnit:Diamagnit

Asosiy o'tishlar:

530 nmd-d
¹A₁ → ¹E, ¹A₂ε=50
370 nmd-d
¹A₁ → ¹E, ¹B₁ε=45
Δo
20,500
cm⁻¹
Racah B (β=0.65)
600
cm⁻¹

Simmetriya buzilishi (Oh → C₄ᵥ), polosa yorilishi

klassikinertd⁶ LSC₄ᵥ
M = 250.44 g/molBatafsil →

[Co(en)3]Cl3

Tris(etilendiamin)kobalt(III) xlorid

[Co(en)₃]³⁺ (sariq)

Konfiguratsiya
d⁶ LS
Yer holati
¹A₁
Rang:sariq-to'q sariq
Struktura:Oktaedr (D₃)
Markazi:Co³⁺
Magnit:Diamagnit

Asosiy o'tishlar:

465 nmd-d
¹A₁ → ¹T₁gε=87
340 nmd-d
¹A₁ → ¹T₂gε=78
Δo
23,300
cm⁻¹
Racah B (β=0.67)
620
cm⁻¹

Xelat effekti, Δ/Λ optik izomerlar (CD spektrda faol)

xelatinertd⁶ LSoptik-izomer
M = 345.52 g/molBatafsil →

[Cr(H2O)6]Cl3

Geksaakvaxrom(III) xlorid

Xrom(III) geksaakva (binafsha)

Konfiguratsiya
d³
Yer holati
⁴A₂g
Rang:binafsha
Struktura:Oktaedr (Oh)
Markazi:Cr³⁺
Magnit:Paramagnit

Asosiy o'tishlar:

575 nmd-d
⁴A₂g → ⁴T₂gε=13
407 nmd-d
⁴A₂g → ⁴T₁g(F)ε=15
265 nmd-d, ko'p LMCT bilan
⁴A₂g → ⁴T₁g(P)ε=kichik
Δo
17,400
cm⁻¹
Racah B (β=0.79)
725
cm⁻¹

d³ — birinchi polosa to'g'ridan-to'g'ri Δo

klassikd³Ohakvakompleks
M = 266.45 g/molBatafsil →

[Cr(NH3)6]Cl3

Geksaamminxrom(III) xlorid

[Cr(NH₃)₆]³⁺ (sariq)

Konfiguratsiya
d³
Yer holati
⁴A₂g
Rang:sariq
Struktura:Oktaedr (Oh)
Markazi:Cr³⁺
Magnit:Paramagnit

Asosiy o'tishlar:

465 nmd-d
⁴A₂g → ⁴T₂gε=40
350 nmd-d
⁴A₂g → ⁴T₁g(F)ε=35
Δo
21,500
cm⁻¹
Racah B (β=0.72)
657
cm⁻¹

NH₃ H₂O ga qaraganda kuchli maydon → Δo↑

klassikd³Ohammin
M = 260.44 g/molBatafsil →

[Ti(H2O)6]3+

Geksaakvatitan(III) ioni

Titan(III) geksaakva (binafsha)

Konfiguratsiya
d¹
Yer holati
²T₂g
Rang:binafsha (och)
Struktura:Oktaedr (Oh, Yan-Teller buzilgan)
Markazi:Ti³⁺
Magnit:Paramagnit

Asosiy o'tishlar:

493 nmd-d
²T₂g → ²Egε=5
Δo
20,300
cm⁻¹

Eng oddiy d¹ holat — Δo to'g'ridan-to'g'ri o'lchanadi

d¹OhYan-Tellereng-oddiy
M = 156.05 g/molBatafsil →

[V(H2O)6]3+

Geksaakvavanadiy(III) ioni

Vanadiy(III) geksaakva (yashil)

Konfiguratsiya
d²
Yer holati
³T₁g(F)
Rang:yashil-havorang
Struktura:Oktaedr (Oh)
Markazi:V³⁺
Magnit:Paramagnit

Asosiy o'tishlar:

562 nmd-d
³T₁g(F) → ³T₂gε=6
389 nmd-d
³T₁g(F) → ³T₁g(P)ε=8
290 nmd-d, LMCT bilan
³T₁g(F) → ³A₂gε=kichik
Δo
18,500
cm⁻¹
Racah B (β=0.72)
620
cm⁻¹

3 ta d–d polosa (F va P terminlariga bo'linadi)

d²Ohakvakompleks
M = 159.02 g/molBatafsil →

[Mn(H2O)6]2+

Geksaakvamangan(II) ioni

Mangan(II) geksaakva (juda och pushti)

Konfiguratsiya
d⁵ HS
Yer holati
⁶A₁g
Rang:juda och pushti (deyarli rangsiz)
Struktura:Oktaedr (Oh)
Markazi:Mn²⁺
Magnit:Paramagnit

Asosiy o'tishlar:

528 nmd-d, spin-taqiq
⁶A₁g → ⁴T₁gε=0.03
433 nmd-d, spin-taqiq
⁶A₁g → ⁴T₂gε=0.04
400 nmd-d, ingichka
⁶A₁g → ⁴A₁g/⁴Egε=0.05
Δo
7,800
cm⁻¹
Racah B (β=0.92)
786
cm⁻¹

Barcha o'tishlar HAM Laport HAM spin taqiqlangan → ε ~ 0.01

d⁵ HSOhspin-taqiqrangsiz
M = 162.98 g/molBatafsil →

[Fe(H2O)6]2+

Geksaakvatemir(II) ioni

Temir(II) geksaakva (och yashil)

Konfiguratsiya
d⁶ HS
Yer holati
⁵T₂g
Rang:och yashil
Struktura:Oktaedr (Oh)
Markazi:Fe²⁺
Magnit:Paramagnit

Asosiy o'tishlar:

962 nmd-d, NIR
⁵T₂g → ⁵Egε=1
Δo
10,400
cm⁻¹

Bir polosa NIR sohada, rang zaif

d⁶ HSOhakvakompleksNIR
M = 161.99 g/molBatafsil →

K4[Fe(CN)6]

Kaliy geksatsianoferrat(II)

Sariq qon tuzi

Konfiguratsiya
d⁶ LS
Yer holati
¹A₁g
Rang:sariq
Struktura:Oktaedr (Oh)
Markazi:Fe²⁺
Magnit:Diamagnit

Asosiy o'tishlar:

320 nmMLCT
¹A₁g → ¹T₁g (MLCT)ε=340
270 nmMLCT
MLCT ikkinchiε=400
Δo
33,800
cm⁻¹
Racah B (β=0.5)
460
cm⁻¹

CN⁻ juda kuchli maydon → Δo bahaybat, MLCT tasmalari

tsianod⁶ LSMLCTdiamagnit
M = 422.39 g/molBatafsil →

K3[Fe(CN)6]

Kaliy geksatsianoferrat(III)

Qizil qon tuzi

Konfiguratsiya
d⁵ LS
Yer holati
²T₂g
Rang:qizil-to'q sariq
Struktura:Oktaedr (Oh)
Markazi:Fe³⁺
Magnit:Paramagnit

Asosiy o'tishlar:

420 nmLMCT
LMCT (CN → Fe)ε=1000
305 nmLMCT
LMCT ikkinchiε=1500
Δo
33,800
cm⁻¹
Racah B (β=0.52)
480
cm⁻¹

Kuchli oksidlovchi, LMCT rangi (qizil)

tsianod⁵ LSLMCToksidlovchi
M = 329.24 g/molBatafsil →

[Fe(SCN)3]

Tris(tiosiyanato-N)temir(III)

Temir(III) rodanid (qon-qizil)

Konfiguratsiya
d⁵ HS
Yer holati
⁶A₁
Rang:qon-qizil
Struktura:Oktaedr (past simmetriya)
Markazi:Fe³⁺
Magnit:Paramagnit

Asosiy o'tishlar:

480 nmLMCT
LMCT (SCN → Fe)ε=5000

Fe³⁺ analitik reagent (Volhard usuli), juda katta ε

tiotsianatod⁵ HSLMCTanalitik
M = 230.08 g/molBatafsil →

[Ni(H2O)6]2+

Geksaakvanikel(II) ioni

Nikel(II) geksaakva (yashil)

Konfiguratsiya
d⁸
Yer holati
³A₂g
Rang:yashil
Struktura:Oktaedr (Oh)
Markazi:Ni²⁺
Magnit:Paramagnit

Asosiy o'tishlar:

1176 nmd-d, NIR
³A₂g → ³T₂gε=2
725 nmd-d
³A₂g → ³T₁g(F)ε=2
395 nmd-d
³A₂g → ³T₁g(P)ε=5
Δo
8,500
cm⁻¹
Racah B (β=0.87)
940
cm⁻¹

3 ta d–d polosa — d⁸ ning klassik namunasi

d⁸Ohakvakompleks3-polosa
M = 174.75 g/molBatafsil →

[Ni(CN)4]2-

Tetratsianonikkolat(II) ioni

[Ni(CN)₄]²⁻ (sariq)

Konfiguratsiya
d⁸ LS
Yer holati
¹A₁g
Rang:sariq
Struktura:Kvadrat-tekis (D₄ₕ)
Markazi:Ni²⁺
Magnit:Diamagnit

Asosiy o'tishlar:

420 nmMLCT
MLCT (Ni → CN)ε=6600
285 nmMLCT
MLCT ikkinchiε=12000

Kuchli maydon CN⁻ → kvadrat tekislik, diamagnit

tsianod⁸ LSMLCTkvadrat-tekis
M = 162.78 g/molBatafsil →

[Cu(H2O)6]2+

Geksaakvamis(II) ioni

Mis(II) geksaakva (havorang)

Konfiguratsiya
d⁹
Yer holati
²Eg (yorilgan)
Rang:havorang
Struktura:Oktaedr (D₄ₕ, kuchli Yan-Teller)
Markazi:Cu²⁺
Magnit:Paramagnit

Asosiy o'tishlar:

794 nmd-d, YT
²Eg → ²T₂g (keng)ε=12
Δo
12,600
cm⁻¹

Kuchli Yan-Teller — keng, asimmetrik polosa (760 va 850 nm yelkalari)

d⁹Yan-Tellerakvakomplekskeng-polosa
M = 171.66 g/molBatafsil →

[Cu(NH3)4]2+

Tetraamminmis(II) ioni

Tetraamminmis(II) (to'q ko'k)

Konfiguratsiya
d⁹
Yer holati
²Eg
Rang:to'q ko'k
Struktura:Kvadrat-tekis buzilgan (D₄ₕ)
Markazi:Cu²⁺
Magnit:Paramagnit

Asosiy o'tishlar:

610 nmd-d, YT
d–d (keng)ε=63
Δo
16,400
cm⁻¹

NH₃ dan Δo yuqoriroq → batoxrom (to'q ko'kga o'zgargan)

d⁹Yan-Telleramminkvadrat-tekis
M = 131.71 g/molBatafsil →

[Co(H2O)6]2+

Geksaakvakobalt(II) ioni

Kobalt(II) geksaakva (pushti)

Konfiguratsiya
d⁷ HS
Yer holati
⁴T₁g(F)
Rang:pushti
Struktura:Oktaedr (Oh)
Markazi:Co²⁺
Magnit:Paramagnit

Asosiy o'tishlar:

1250 nmd-d, NIR
⁴T₁g(F) → ⁴T₂gε=2
625 nmd-d, ikki elektron
⁴T₁g(F) → ⁴A₂gε=5
515 nmd-d
⁴T₁g(F) → ⁴T₁g(P)ε=5
Δo
9,200
cm⁻¹
Racah B (β=0.85)
825
cm⁻¹

Pushti rang — [CoCl₄]²⁻ ga qaraganda kam intensiv

d⁷ HSOhakvakomplekspushti
M = 165.05 g/molBatafsil →

[CoCl4]2-

Tetraxlorokobaltat(II) ioni

[CoCl₄]²⁻ (to'q ko'k)

Konfiguratsiya
d⁷
Yer holati
⁴A₂
Rang:to'q ko'k
Struktura:Tetraedr (Td)
Markazi:Co²⁺
Magnit:Paramagnit

Asosiy o'tishlar:

660 nmd-d, Laport-ruxsat
⁴A₂ → ⁴T₁(P)ε=600
Δt
3,300
cm⁻¹
Racah B (β=0.73)
710
cm⁻¹

Td (i markaz yo'q) → Laport ruxsat → ε juda katta (600)! Rang zaif emas

d⁷TdLaport-ruxsatto'q-ko'k
M = 200.75 g/molBatafsil →

cis-[Pt(NH3)2Cl2]

sis-Diammindixloroplatina(II)

Sisplatin (saraton dori)

Konfiguratsiya
d⁸ LS
Yer holati
¹A₁
Rang:sariq
Struktura:Kvadrat-tekis (C₂ᵥ)
Markazi:Pt²⁺
Magnit:Diamagnit

Asosiy o'tishlar:

365 nmd-d
d–d (yelka)ε=30
301 nmLMCT
LMCT (Cl → Pt)ε=130

Saraton dori (1978 FDA), DNK ga bog'lanadi

sisplatinkvadrat-tekisd⁸ LSbiologik
M = 300.05 g/molBatafsil →

trans-[Pt(NH3)2Cl2]

trans-Diammindixloroplatina(II)

Transplatin (klinik faol emas)

Konfiguratsiya
d⁸ LS
Yer holati
¹A₁g
Rang:och sariq
Struktura:Kvadrat-tekis (D₂ₕ)
Markazi:Pt²⁺
Magnit:Diamagnit

Asosiy o'tishlar:

331 nmd-d
d–dε=15
279 nmLMCT
LMCTε=70

D₂ₕ (i markaz bor) → Laport taqiqlash → ε kamroq

transplatinkvadrat-tekisd⁸ LSD₂ₕ
M = 300.05 g/molBatafsil →

KMnO4

Kaliy permanganat

Permanganat (binafsha)

Konfiguratsiya
d⁰
Yer holati
¹A₁
Rang:to'q binafsha
Struktura:Tetraedr (Td)
Markazi:Mn⁷⁺
Magnit:Diamagnit

Asosiy o'tishlar:

525 nmLMCT
LMCT (O → Mn)ε=2400
545 nmLMCT
LMCT ikkinchiε=2300

d⁰ — d–d o'tishlar YO'Q! Rang faqat LMCT dan

d⁰LMCTTdoksoanionklassik-misol
M = 158.03 g/molBatafsil →

K2Cr2O7

Kaliy dixromat

Dixromat (to'q sariq)

Konfiguratsiya
d⁰
Yer holati
¹A₁
Rang:to'q sariq-qizil
Struktura:Ikki tetraedr (Cr₂O₇²⁻)
Markazi:Cr⁶⁺
Magnit:Diamagnit

Asosiy o'tishlar:

350 nmLMCT
LMCT (O → Cr)ε=3160
257 nmLMCT
LMCT ikkinchiε=3400

d⁰ — Cr⁶⁺ ning yuqori zaryadi juda kuchli LMCT ni beradi

d⁰LMCTCr(VI)oksidlovchi
M = 294.18 g/molBatafsil →

[Fe(C5H5)2]

bis(η⁵-siklopentadienil)temir(II)

Ferrosen (to'q sariq)

Konfiguratsiya
d⁶ LS
Yer holati
¹A₁g
Rang:to'q sariq
Struktura:Sendvich (D₅d)
Markazi:Fe²⁺
Magnit:Diamagnit

Asosiy o'tishlar:

440 nmd-d + MLCT
d–d + MLCT aralashε=91
325 nmIL
π→π* (Cp ligandi)ε=55

Metallosen kimyoning asosi (1951, Kealy-Pauson)

metallosend⁶ LS18-elektronsendvich
M = 186.04 g/molBatafsil →

[Ru(bpy)3]2+

Tris(2,2'-bipiridin)ruteniy(II) ioni

Ruteniy-tris-bipiridil (to'q qizil)

Konfiguratsiya
d⁶ LS
Yer holati
¹A₁
Rang:to'q qizil-to'q sariq
Struktura:Oktaedr (D₃)
Markazi:Ru²⁺
Magnit:Diamagnit

Asosiy o'tishlar:

452 nmMLCT
MLCT (Ru → bpy π*)ε=14600
285 nmIL
IL π→π* (bpy)ε=87000
Δo
28,600
cm⁻¹
Racah B (β=0.83)
590
cm⁻¹

Quyosh batareya, fotokataliz, DSSC (Grätzel), lyuminessent

d⁶ LSMLCTfotokatalizpolipyridil
M = 570.58 g/molBatafsil →

[Zn(OH)4]2-

Tetragidroksosinkat(II) ioni

Tsinkat (rangsiz)

Konfiguratsiya
d¹⁰
Yer holati
¹A₁
Rang:rangsiz
Struktura:Tetraedr (Td)
Markazi:Zn²⁺
Magnit:Diamagnit

Asosiy o'tishlar:

—d-d yo'q
d–d YO'Qε=0

d¹⁰ — barcha d-orbital to'la → d–d o'tish YO'Q → rangsiz

d¹⁰rangsizTdamfoter
M = 133.41 g/molBatafsil →

Spektral parametrlarni taqqoslash

KompleksdⁿΔo yoki Δt (cm⁻¹)B (cm⁻¹)βO'tish turi
[Co(NH3)6]Cl3d⁶ LS22,9006150.66d-d
[Co(NH3)5Cl]Cl2d⁶ LS20,5006000.65d-d
[Co(en)3]Cl3d⁶ LS23,3006200.67d-d
[Cr(H2O)6]Cl3d³17,4007250.79d-d
[Cr(NH3)6]Cl3d³21,5006570.72d-d
[Ti(H2O)6]3+d¹20,300——d-d
[V(H2O)6]3+d²18,5006200.72d-d
[Mn(H2O)6]2+d⁵ HS7,8007860.92d-d (spin-taqiq)
[Fe(H2O)6]2+d⁶ HS10,400——d-d
K4[Fe(CN)6]d⁶ LS33,8004600.5MLCT
K3[Fe(CN)6]d⁵ LS33,8004800.52LMCT
[Ni(H2O)6]2+d⁸8,5009400.87d-d
[Cu(H2O)6]2+d⁹12,600——d-d
[Cu(NH3)4]2+d⁹16,400——d-d
[Co(H2O)6]2+d⁷ HS9,2008250.85d-d