the expected values.

UV-Vis spectroscopy

NABIL KORIR showed a red-shifted absorption at 462 nm,

indicating metal-to-ligand charge transfer

4-Methoxy-2-Nitroaniline Ferrocenyl driven by enhanced π-conjugation.

Derivative These results highlight the versatility of

diazonium chemistry in designing

compounds with tailored optical and

ABSTRACT electronic properties, promising applications

This study presents the synthesis and in molecular electronics and catalysis.

characterization of a 4-methoxy-2-

nitroaniline ferrocenyl derivative via

diazonium chemistry, enabling efficient CHEMICAL CONTEXT

functionalization of ferrocene. The reaction The diazonium-based coupling has emerged

yielded a reddish-brown solid (0.18 g, as a versatile reaction for carbon-carbon

10.25%) with a melting point of 345.5– bond formation and is extensively utilized in

348.6 K. synthesizing functionalized aromatic

Spectroscopic analysis confirmed the compounds1,2Diazonium salts' high

structure and electronic properties. ¹H NMR reactivity and straightforward preparation

revealed signals at δ 4.05 ppm (Cp ring) and make this method highly accessible to

δ 4.19 ppm (methoxy protons), reflecting the synthetic chemists. We employed this

electronic effects of the substituents. IR coupling protocol to synthesize a ferrocenyl

bands at 1621.42 cm⁻¹ (C=C), 1498.87 cm⁻¹ derivative by reacting 4-methoxy-2-

(N–O), and 1270.76 cm⁻¹ (C–O) matched nitroaniline-derived diazonium salt with
ferrocene under mild conditions (Figure.1). demonstrates the utility of diazonium-based

This approach effectively integrates coupling for creating structurally diverse

diazotization and electrophilic aromatic organometallic frameworks.

substitution to construct the desired aryl- Using ferrocene's electron-rich

ferrocenyl product. cyclopentadienyl rings ensures efficient

electrophilic aromatic substitution, while the

stability of the diazonium intermediate

minimizes side reactions. These attributes

make diazonium-based coupling a scalable

method for synthesizing advanced

Fig .1 Synthesis of a 4-methoxy-2-nitroaniline ferrocenyl

derivative
organometallic compounds, further

underscoring its value in modern synthetic

Ferrocenyl derivatives are of significant
chemistry.
interest due to their redox activity and

structural versatility. Functionalized

SPECTROSCOPY COMMENTARY
ferrocenes, such as the one synthesized here,

have been widely applied in catalysis,

molecular electronics, and advanced

materials. Similar derivatives have been

studied for their electronic communication

properties and stability, particularly in

applications requiring precise modulation of

redox potentials3,4,5. The selective mono-

functionalization achieved in this reaction

Fig .2 1H NMR (CDCl3, 25 OC, 60 MHz): δ =4.05 (s,5H, Ar- caused by the substitution, resulting in
CH5),4.19 (s,3H, CH3),4.42 (s,2H, CH2),4.68 (s,2H, CH2),6.96

(s,1H, Ar-H),7.65 (s, 1H, Ar-H),7.82 (s,1H, Ar-H).

chemically distinct proton environments.

The aromatic region of the spectrum

contains singlets at δ 6.96, 7.65, and 7.82

The ¹H NMR spectrum (Figure 2) displays a ppm. These chemical shifts are consistent

singlet at δ 4.05 ppm, integrating for five with aromatic protons experiencing varying

protons, indicative of the unsubstituted electronic effects from substituents. The

cyclopentadienyl (Cp) ring. This singlet methoxy group, acting as an electron-

arises from the high symmetry of the five donating substituent, and the nitro group,

coordinated Cp ring, characteristic of acting as an electron-withdrawing

ferrocene complexes. substituent, collectively influence the

Another singlet at δ 4.19 ppm integrates for electron density on the aromatic ring,

three protons, corresponding to the methyl altering the chemical shifts

group of a methoxy (-OCH₃) substituent.

The observed downfield shift, relative to the

typical range of methoxy protons (δ 3.7–4.0

ppm), suggests deshielding due to an

adjacent electron-withdrawing group3. Two

additional singlets at δ 4.42 and 4.68 ppm,

each integrating for two protons, are

assigned to the substituted Cp ring. These

signals reflect the disruption of symmetry

IR SPECTROSCOPY Another significant band appeared

at 1498.87 cm⁻¹, attributed to a nitro group's

asymmetric (N–O) stretching vibration. The

presence of this band serves as a definitive

indicator of nitro functionality, a crucial

structural component of the compound.

Additionally, a (C–O) stretching vibration

was observed at 1270.76 cm⁻¹, consistent

with the presence of an ether group,

Fig .3 IR (ATR): ν = 1621.42 (AR-C=C), 1498.87 (N-O), 1270.76 specifically an aromatic ether, which
(C-O) cm-1.
supports the assignment of the methoxy

substituent on the aromatic ring.

The compound's structural features were

first examined using ATR spectroscopy

(Figure.3) which provided distinct and well-

defined absorption bands at 1621.42 cm⁻¹,

corresponding to the aromatic (C=C)

stretching vibrations, confirming an

aromatic system's presence. This band is

characteristic of the π-conjugated structure

typical in aromatic compounds, reflecting

the resonance stabilization within the Fig .4 IR (CH2Cl2): ν =1625 (AR-C=C),1510 (N-O),1279 (C-O)

cm-1.
aromatic ring.
To further investigate the structural UV-VIS SPECTROSCOPY

consistency and assess any environmental

effects on the vibrational frequencies, the IR

Wavelength vs Abs
spectrum (Figure 4) was also recorded in a
3.5
3
CH₂Cl₂ solvent environment. In CH₂Cl₂, 2.5
2

Abs(A)
the same characteristic absorption bands 1.5
1
were detected, although with slight shifts: 0.5
0
-0.5300 400 500 600 700 800 900
the aromatic (C=C) stretching band shifted
Wavelength(λ)
to 1625 cm⁻¹, the (N–O) stretching band
Run 3(1:9) Run 1 (1:9/2.3) Run 2(1:9/1:4)
to 1510 cm⁻¹, and the (C–O) stretching band
Fig 5. Wavelength vs Absorbance. Maximum absorbance at 462
to 1279 cm⁻¹. These small shifts are
nm

attributed to solvent interactions, which can

Conc Vs Abs
slightly alter the electronic environment of
1

the functional groups and, consequently, f(x)0.8

= 2983.876009895 x − 0.02091084624
R² 0.6
= 0.962277008155813
Abs(A)

their vibrational frequencies. 4 Nevertheless, 0.4

0.2
the overall consistency of the absorption 0
0 0.0001 0.0002 0.0003 0.0004
bands between the ATR and CH₂Cl₂ spectra Conc(M)

underscores the functional group

Abs Linear (Abs )
assignments' stability, confirming the
Fig 6. Concentration vs Absorbance. (ε = 2983.9 M⁻¹cm⁻¹).

compound's structural integrity across Conc(M) Abs(A)

different media.
0.00029661 0.85571357

9.8871E-05 0.34998709

7.4153E-05 0.13290463
Table 1. Concentration vs Absorbance electron density via inductive and resonance

effects, establishing a significant push-pull

The UV-Vis spectrum (Figure.5) of the electronic interaction.
ferrocene derivative reveals a pronounced The push-pull effect enhances the charge
absorption band at 462 nm (ε = 2983.9 transfer transition by stabilizing the excited
M⁻¹cm⁻¹), which is attributed to a metal-to- state and lowering the energy required for
ligand charge transfer transition. This band electronic excitation, thereby shifting the
is characteristic of organometallic absorption to a longer wavelength. The high
complexes, where the central iron atom in molar absorptivity (ε = 2983.9 M⁻¹cm⁻¹)
the ferrocene core donates electron density reflects the overlap between the metal d-
to the π-accepting orbitals of the coordinated orbitals and the π-system, consistent with a
ligands or substituents. highly delocalized electron density across

the aromatic system. These observations

The observed red shift in the absorption support the presence of significant
maximum, relative to unsubstituted conjugation and electronic delocalization,
ferrocene, indicates an extended conjugated which are key contributors to the
system. This effect is attributed to the compound’s optical properties.
electronic influence of the substituents: a

methoxy group acting as an electron-

donating substituent and a nitro group

functioning as a strong electron-withdrawing

substituent. The methoxy group increases

electron density in the π-system through

resonance, while the nitro group withdraws

LITERATURE SURVEY introducing chromophoric functionalities in

material sciences 7. The modifications

The synthesis and study of 4-methoxy-2- enhance ferrocene derivatives' optical and

nitroaniline ferrocenyl derivatives build electronic properties, broadening their

upon advancements in diazonium coupling application potential.

reactions and the functionalization of Ferrocene derivatives' structural versatility

ferrocene, a key organometallic scaffold. As and redox activity continue to make them

Gomberg and Bachmann demonstrated, valuable in catalysis and electronics. Paul et

Diazonium salts are foundational in forming al. demonstrated that substituents on the

aryl-aryl bonds, enabling selective and cyclopentadienyl rings can significantly alter

efficient aromatic substitutions. Their work redox potentials, tailoring ferrocene

established the utility of diazonium derivatives for specific applications such as

intermediates in modifying aromatic molecular electronics and catalysis 8.

systems, paving the way for diverse Similarly, Vogel et al. illustrated the

applications in synthetic chemistry 6 adaptability of ferrocene's sandwich

This study's application of diazonium-based structure through successful derivatization

electrophilic aromatic substitution using acylation and alkylation, further

effectively incorporates electron-donating underscoring the chemical flexibility of

methoxy and electron-withdrawing nitro ferrocene derivatives9

groups into ferrocene's aromatic framework. The UV-Vis spectroscopy of the synthesized

This strategy aligns with the findings of compound revealed a red-shifted absorption

Chng et al., who highlighted the robustness maximum at 462 nm, indicative of a push-

of diazonium coupling reactions for pull interaction between the methoxy and
nitro substituents. This observation is structurally similar ferrocene derivatives, as

consistent with Sano et al.'s findings on the highlighted in studies on diazonium-coupled

electronic effects of substituents in ferrocene complexes, supporting the assignment of the

derivatives, which play a critical role in vibrational features and structural integrity

enhancing the conjugation and charge of the synthesized compound 8,9

transfer properties of organometallic

complexes in semiconductors10 PROCEDURE

Electrochemical studies further A 100 mL round-bottom flask was charged

demonstrated the interplay of methoxy and with 4-methoxy-2-nitroaniline (0.74 g, 4.000

nitro substituents in stabilizing the iron mmol) and 10 mL of deionized water. A

center's electronic environment while PTFE-coated stir bar was added, and the

introducing novel redox behaviors. Similar mixture was stirred while concentrated

trends were observed in the work of Paul et sulfuric acid (1.12 mL) was added dropwise.

al., where alkyl ferrocene derivatives As the aniline derivative dissolved in the

exhibited tunable redox potentials dependent acidic medium, the solution became clear

on their electronic configurations, and developed a light-yellow tint. The flask

highlighting their utility in advanced was placed in an ice-water bath, and a low

molecular applications 11 temperature was maintained, increasing the

IR spectroscopy provided complementary solution's viscosity.

structural insights, with characteristic

stretches confirming the presence of In a separate 50 mL Erlenmeyer flask,

methoxy and nitro functionalities. These sodium nitrite (0.34 g, 4.870 mmol) was

findings align well with reports on dissolved in 3.20 mL of deionized water and
cooled in an ice-water bath. The sodium

nitrite solution formed a clear, colorless A 100 mL round-bottom flask was charged

solution. While stirring the aniline- with ferrocene (0.94 g, 4.060 mmol)

containing solution, the sodium nitrite and 4.16 mL of 1,2-dichloroethane, followed

solution was added dropwise over one by the addition of 1.60 mL of glacial acetic

minute. The reaction mixture gradually acid and 0.21 g of sodium acetate (2.536

changed to light brown, and mild bubbling mmol). The ferrocene dissolved, forming a

was observed as nitrogen gas was released, bright orange solution. The mixture was

indicating the formation of the diazonium stirred for 20 minutes to ensure complete

salt. The mixture was stirred for 10 minutes dissolution. The diazonium salt solution was

in the ice-water bath to complete the then added dropwise to the stirring ferrocene

diazonium salt formation. solution in the ice-water bath. During the

addition, the color of the ferrocene solution

A separate solution of urea (0.06 g, 0.933 darkened slightly. The reaction mixture was

mmol) was prepared by dissolving it in 3.20 stirred in the ice water bath for 30 minutes

mL of deionized water and cooling it in a and then left to stir until the next lab

water bath. After stirring the diazonium salt period,7 days later. The color of the reaction

solution for 10 minutes, the urea solution mixture darkened further, indicating the

was added dropwise to neutralize any excess progress of the reaction.

nitrous acid. The bubbling slowed and then

ceased. The reaction mixture was stirred for The reaction mixture was transferred to

an additional 20 minutes in an ice water bath a separatory funnel, and the organic layer

to ensure the stability of the diazonium salt. was extracted three times with 20 mL
portions of dichloromethane; after adding fractions. ¹H NMR analysis was used to

dichloromethane, two clear layers formed, distinguish the fractions, confirming the

with the organic layer appearing reddish- separation of the desired product from

brown and aqueous pale blue. The combined impurities. Four purified fractions were

organic layers were washed three times combined, and further purification was

with 20 mL portions of deionized water to achieved through sublimation, enhancing the

remove any residual acidic impurities. The purity of the product. The final pure product,

organic phase was dried over anhydrous a reddish-brown solid with a mass of 0.18 g,

magnesium sulfate for 15 minutes. The 10.25% yield, and a melting point range was

drying agent clumped, and the organic 345.5-348.6 K. It was further characterized

solution became clear. The solution was by IR spectroscopy and electronic

filtered to remove the drying agent, and the absorption spectroscopy. 1H NMR (CDCl3,

solvent was removed by passing a gentle 25 OC, 60 MHz): δ =4.05 (s,5H, Ar-

airflow over the liquid, yielding a reddish- CH5),4.19 (s,3H, CH3),4.42 (s,2H, CH2),4.68

brown solid as the crude product. (s,2H, CH2),6.96 (s,1H, Ar-H),7.65 (s, 1H,

Ar-H),7.82 (s,1H, Ar-H).IR (ATR): ν =

The crude product was purified 1621.42 (AR-C=C), 1498.87 (N-O), 1270.76

using column chromatography on silica gel. (C-O) cm-1. IR (CH2Cl2): ν =1625 (Ar-

The column was eluted starting with hexane, C=C),1510 (N-O),1279 (C-O) cm-1. UV Vis

gradually increasing the polarity with ethyl (THF, 25 oC): λ max = 462 nm, ε = 2983.9

acetate and passing a gentle stream of air M⁻¹cm⁻¹, MP = 345.5-348.6 K.

above it. The product was observed to elute

in orange, yellow, reddish-brown, and green

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